Characterization of Coconut Oil Fractions Obtained from Solvent Fractionation Using Acetone.

PubMed

Sonwai, Sopark; Rungprasertphol, Poonyawee; Nantipipat, Nantinee; Tungvongcharoan, Satinee; Laiyangkoon, Nantikan

2017-09-01

This work was aimed to study the solvent fraction of coconut oil (CNO). The fatty acid and triacylglycerol compositions, solid fat content (SFC) and the crystallization properties of CNO and its solid and liquid fractions obtained from fractionation at different conditions were investigated using various techniques. CNO was dissolved in acetone (1:1 w/v) and left to crystallize isothermally at 10°C for 0.5, 1 and 2 h and at 12°C for 2, 3 and 6 h. The solid fractions contained significantly lower contents of saturated fatty acids of ≤ 10 carbon atoms but considerably higher contents of saturated fatty acids with > 12 carbon atoms with respect to those of CNO and the liquid fractions. They also contained higher contents of high-melting triacylglycerol species with carbon number ≥ 38. Because of this, the DSC crystallization onset temperatures and the crystallization peak temperatures of the solid fractions were higher than CNO and the liquid fractions. The SFC values of the solid fractions were significantly higher than CNO at all measuring temperatures before reaching 0% just below the body temperature with the fraction obtained at 12°C for 2 h exhibiting the highest SFC. On the contrary, the SFC values of the liquid fractions were lower than CNO. The crystallization duration exhibited strong influence on the solid fractions. There was no effect on the crystal polymorphic structure possibly because CNO has β'-2 as a stable polymorph. The enhanced SFC of the solid fractions would allow them to find use in food applications where a specific melting temperature is desired such as sophisticated confectionery fats, and the decreased SFC of the liquid fractions would provide them with a higher cold stability which would be useful during extended storage time.

Evidence for Cyclical Fractional Crystallization, Recharge, and Assimilation in Basalts of the Kimama Core, Central Snake River Plain, Idaho: A 5.5-million-year Highlight Reel of Petrogenetic processes in a Mid-Crustal Sill Complex

NASA Astrophysics Data System (ADS)

Potter, Katherine E.; Shervais, John W.; Christiansen, Eric H.; Vetter, Scott K.

2018-02-01

Basalts erupted in the Snake River Plain of central Idaho and sampled in the Kimama drill core link eruptive processes to the construction of mafic intrusions over 5.5 Ma. Cyclic variations in basalt composition reveal temporal chemical heterogeneity related to fractional crystallization and the assimilation of previously-intruded mafic sills. A range of compositional types are identified within 1912 m of continuous drill core: Snake River olivine tholeiite (SROT), low K SROT, high Fe-Ti, and evolved and high K-Fe lavas similar to those erupted at Craters of the Moon National Monument. Detailed lithologic and geophysical logs document 432 flow units comprising 183 distinct lava flows and 78 flow groups. Each lava flow represents a single eruptive episode, while flow groups document chemically and temporally related flows that formed over extended periods of time. Temporal chemical variation demonstrates the importance of source heterogeneity and magma processing in basalt petrogenesis. Low-K SROT and high Fe-Ti basalts are genetically related to SROT as, respectively, hydrothermally-altered and fractionated daughters. Cyclic variations in the chemical composition of Kimama flow groups are apparent as 21 upward fractionation cycles, six recharge cycles, eight recharge-fractionation cycles, and five fractionation-recharge cycles. We propose that most Kimama basalt flows represent typical fractionation and recharge patterns, consistent with the repeated influx of primitive SROT parental magmas and extensive fractional crystallization coupled with varying degrees of assimilation of gabbroic to ferrodioritic sills at shallow to intermediate depths over short durations. Trace element models show that parental SROT basalts were generated by 5-10% partial melting of enriched mantle at shallow depths above the garnet-spinel lherzolite transition. The distinctive evolved and high K-Fe lavas are rare. Found at four depths, 319 m, 1045 m, 1078 m, and 1189 m, evolved and high K-Fe flows are compositionally unrelated to SROT magmas and represent highly fractionated basalt, probably accompanied by crustal assimilation. These evolved lavas may be sourced from the Craters of the Moon/Great Rift system to the northeast. The Kimama drill core is the longest record of geochemical variation in the central Snake River Plain and reinforces the concept of magma processing in a layered complex.

Variscan potassic dyke magmatism of durbachitic affinity at the southern end of the Bohemian Massif (Lower Austria)

NASA Astrophysics Data System (ADS)

Zeitlhofer, Helga; Grasemann, Bernhard; Petrakakis, Konstantin

2016-06-01

Dykes in the Strudengau area (SW Moldanubian Zone, Austria) can be mineralogically divided into lamprophyres (spessartites and kersantites) and felsic dykes (granite porphyries, granitic dykes and pegmatoid dykes). Geochemical analyses of 11 lamprophyres and 7 felsic dykes show evidence of fractional crystallization. The lamprophyres are characterized by metaluminous compositions, intermediate SiO2 contents and high amounts of MgO and K2O; these rocks have high Ba (800-3000 ppm) and Sr (250-1000 ppm) contents as well as an enrichment of large-ion lithophile elements over high field strength elements, typical for enriched mantle sources with variable modifications due to fractionation and crustal contamination. This geochemical signature has been reported from durbachites (biotite- and K feldspar-rich mela-syenites particularly characteristic of the Variscan orogen in Central Europe). For most major elements, calculated fractionation trends from crystallization experiments of durbachites give an excellent match with the data from the Strudengau dykes. This suggests that the lamprophyres and felsic dykes were both products of fractional crystallization and subsequent magma mixing of durbachitic and leucogranitic melts. Rb-Sr geochronological data on biotite from five undeformed kersantites and a locally deformed granite porphyry gave cooling ages of c. 334-318 Ma, indicating synchronous intrusion of the dykes with the nearby outcropping Weinsberger granite (part of the South Bohemian Batholith, c. 330-310 Ma). Oriented matrix biotite separated from the locally deformed granite porphyry gave an Rb-Sr age of c. 318 Ma, interpreted as a deformation age during extensional tectonics. We propose a large-scale extensional regime at c. 320 Ma in the Strudengau area, accompanied by plutonism of fractionated magmas of syncollisional mantle-derived sources, mixed with crustal components. This geodynamic setting is comparable to other areas in the Variscan belt documenting an orogenic wide extension by the end of the Carboniferous.

DDA Computations of Porous Aggregates with Forsterite Crystals: Effects of Crystal Shape and Crystal Mass Fraction

NASA Technical Reports Server (NTRS)

Wooden, Diane H.; Lindsay, Sean S.; Harker, David; Woodward, Charles; Kelley, Michael S.; Kolokolova, Ludmilla

2015-01-01

Porous aggregate grains are commonly found in cometary dust samples and are needed to model cometary IR spectral energy distributions (SEDs). Models for thermal emissions from comets require two forms of silicates: amorphous and crystalline. The dominant crystal resonances observed in comet SEDs are from Forsterite (Mg2SiO4). The mass fractions that are crystalline span a large range from 0.0 < or = fcrystal < or = 0.74. Radial transport models that predict the enrichment of the outer disk (>25 AU at 1E6 yr) by inner disk materials (crystals) are challenged to yield the highend-range of cometary crystal mass fractions. However, in current thermal models, Forsterite crystals are not incorporated into larger aggregate grains but instead only are considered as discrete crystals. A complicating factor is that Forsterite crystals with rectangular shapes better fit the observed spectral resonances in wavelength (11.0-11.15 microns, 16, 19, 23.5, 27, and 33 microns), feature asymmetry and relative height (Lindley et al. 2013) than spherically or elliptically shaped crystals. We present DDA-DDSCAT computations of IR absorptivities (Qabs) of 3 micron-radii porous aggregates with 0.13 < or = fcrystal < or = 0.35 and with polyhedral-shaped Forsterite crystals. We can produce crystal resonances with similar appearance to the observed resonances of comet Hale- Bopp. Also, a lower mass fraction of crystals in aggregates can produce the same spectral contrast as a higher mass fraction of discrete crystals; the 11micron and 23 micron crystalline resonances appear amplified when crystals are incorporated into aggregates composed otherwise of spherically shaped amorphous Fe-Mg olivines and pyroxenes. We show that the optical properties of a porous aggregate is not linear combination of its monomers, so aggregates need to be computed. We discuss the consequence of lowering comet crystal mass fractions by modeling IR SEDs with aggregates with crystals, and the implications for radial transport models of our protoplanetary disk.

The "New Polyethylene Glycol Dilemma": Polyethylene Glycol Impurities and Their Paradox Role in mAb Crystallization.

PubMed

Hildebrandt, Christian; Joos, Lea; Saedler, Rainer; Winter, Gerhard

2015-06-01

Polyethylene glycols (PEG) represent the most successful and frequently applied class of excipients used for protein crystallization. PEG auto-oxidation and formation of impurities such as peroxides and formaldehydes that foster protein drug degradation is known. However, their effect on mAb crystallization has not been studied in detail before. During the present study, a model IgG1 antibody (mAb1) was crystallized in PEG solutions. Aggregate formation was observed during crystallization and storage that was ascribed to PEG degradation products. Reduction of peroxide and formaldehyde levels prior to crystallization by vacuum and freeze-drying was investigated for its effect on protein degradation. Vacuum drying was superior in removal of peroxides but inferior in reducing formaldehyde residues. Consequently, double purification allowed extensive removal of both impurities. Applying of purified PEG led to 50% lower aggregate fractions. Surprisingly, PEG double purification or addition of methionine prior to crystallization prevented crystal formation. With increased PEG concentration or spiking with peroxides and formaldehydes, crystal formation could be recovered again. With these results, we demonstrate that minimum amounts of oxidizing impurities and thus in consequence chemically altered proteins are vital to initiate mAb1 crystallization. The present study calls PEG as good precipitant for therapeutic biopharmaceuticals into question. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Mushy magma processes in the Tuolumne intrusive complex, Sierra Nevada, California

NASA Astrophysics Data System (ADS)

Memeti, V.; Paterson, S. R.

2012-12-01

Debates continue on the nature of volcanic-plutonic connections and the mechanisms of derivation of large volcanic eruptions, which require large volumes of magma to be readily available within a short period of time. Our focus to understand these magma plumbing systems has been to study the nature of their mid-to upper crustal sections, such as the 1,000 km2, 95-85 Ma old Tuolumne intrusive complex in the Sierra Nevada, California, USA. The Tuolumne intrusive complex is a great example where the magma mush model nicely explains observations derived from several datasets. These data suggest that a magma mush body was present and may have been quite extensive especially at times when the Tuolumne intrusive complex was undergoing waxing periods of magmatism (increased magma input), which alternated with waning periods of magmatism (decreased magma addition) and thus a smaller mush body, essentially mimicking in style periodic flare-ups and lulls at the arc scale. During waxing stages, magma erosion and mixing were the dominant processes, whereas waning stages allowed mush domains to continue to undergo fractional crystallization creating additional compositional variations. Over time, the imprint left behind by previous waxing and waning stages was partly overprinted, but individual crystals successfully recorded the compositions of these earlier magmas. Waxing periods in the Tuolumne intrusive complex during which large magma mush bodies formed are supported by the following evidence: 1) Hybrid units and gradational contacts are commonly present between major Tuolumne units. 2) CA-TIMS U/Pb zircon geochronology data demonstrate that antecrystic zircon recycling took place unidirectional from the oldest, marginal unit toward the younger, interior parts of the intrusion, where increasing zircon age spread encompasses the entire age range of the Tuolumne. 3) The younger, interior units also show an increasing scatter and complexity in geochemical element and isotope whole rock data. 4) Single mineral geochemistry suggests that this increased heterogeneity in the interior of the complex is likely caused by the presence of mixed mineral populations that acquired their compositional zoning in magmas different than the one they most recently crystallized in. 5) Mixed mineral populations have also been found in places of local magma mixing (e.g., tubes and troughs), and 6) oscillatory trace element zoning in K-feldspar phenocrysts most likely represents magma replenishment. All of these phenomena suggest a fairly dynamic environment of magma replenishment, magmatic erosion and extensive mixing at the locus of chamber growth. Magma replenishment subsided after episodic flare-ups and the magma mush dominantly underwent fractional crystallization and magmatic fabric formation during waning stages, when it was capable of preserving the evidence at map to crystal scale, lacking any later overprint by mixing. Fractionation related evidence is apparent in the presence of 1) map to outcrop scale leucogranite lenses and dikes in all major Tuolumne units (including the Johnson Peak granite itself), 2) the concentric compositional zonation of magmatic lobes (e.g., southern Half Dome lobe), 3) local crystal accumulations and widespread schlieren, and 4) fractionation related single mineral element zoning.

Magmatic evolution of Panama Canal volcanic rocks: A record of arc processes and tectonic change

PubMed Central

Cardona, Agustin; Montes, Camilo; Foster, David; Jaramillo, Carlos

2017-01-01

Volcanic rocks along the Panama Canal present a world-class opportunity to examine the relationship between arc magmatism, tectonic forcing, wet and dry magmas, and volcanic structures. Major and trace element geochemistry of Canal volcanic rocks indicate a significant petrologic transition at 21–25 Ma. Oligocene Bas Obispo Fm. rocks have large negative Nb-Ta anomalies, low HREE, fluid mobile element enrichments, a THI of 0.88, and a H2Ocalc of >3 wt. %. In contrast, the Miocene Pedro Miguel and Late Basalt Fm. exhibit reduced Nb-Ta anomalies, flattened REE curves, depleted fluid mobile elements, a THI of 1.45, a H2Ocalc of <1 wt. %, and plot in mid-ocean ridge/back-arc basin fields. Geochemical modeling of Miocene rocks indicates 0.5–0.1 kbar crystallization depths of hot (1100–1190°C) magmas in which most compositional diversity can be explained by fractional crystallization (F = 0.5). However, the most silicic lavas (Las Cascadas Fm.) require an additional mechanism, and assimilation-fractional-crystallization can reproduce observed compositions at reasonable melt fractions. The Canal volcanic rocks, therefore, change from hydrous basaltic pyroclastic deposits typical of mantle-wedge-derived magmas, to hot, dry bi-modal magmatism at the Oligocene-Miocene boundary. We suggest the primary reason for the change is onset of arc perpendicular extension localized to central Panama. High-resolution mapping along the Panama Canal has revealed a sequence of inward dipping maar-diatreme pyroclastic pipes, large basaltic sills, and bedded silicic ignimbrites and tuff deposits. These volcanic bodies intrude into the sedimentary Canal Basin and are cut by normal and subsequently strike-slip faults. Such pyroclastic pipes and basaltic sills are most common in extensional arc and large igneous province environments. Overall, the change in volcanic edifice form and geochemistry are related to onset of arc perpendicular extension, and are consistent with the idea that Panama arc crust fractured during collision with South America forming the observed Canal extensional zone. PMID:28489866

Can Fractional Crystallization of a Lunar Magma Ocean Produce the Lunar Crust?

NASA Technical Reports Server (NTRS)

Rapp, Jennifer F.; Draper, David S.

2013-01-01

New techniques enable the study of Apollo samples and lunar meteorites in unprecedented detail, and recent orbital spectral data reveal more about the lunar farside than ever before, raising new questions about the supposed simplicity of lunar geology. Nevertheless, crystallization of a global-scale magma ocean remains the best model to account for known lunar lithologies. Crystallization of a lunar magma ocean (LMO) is modeled to proceed by two end-member processes - fractional crystallization from (mostly) the bottom up, or initial equilibrium crystallization as the magma is vigorously convecting and crystals remain entrained, followed by crystal settling and a final period of fractional crystallization [1]. Physical models of magma viscosity and convection at this scale suggest that both processes are possible. We have been carrying out high-fidelity experimental simulations of LMO crystallization using two bulk compositions that can be regarded as end-members in the likely relevant range: Taylor Whole Moon (TWM) [2] and Lunar Primitive Upper Mantle (LPUM) [3]. TWM is enriched in refractory elements by 1.5 times relative to Earth, whereas LPUM is similar to the terrestrial primitive upper mantle, with adjustments made for the depletion of volatile alkalis observed on the Moon. Here we extend our earlier equilibrium-crystallization experiments [4] with runs simulating full fractional crystallization

Control of crystal growth in water purification by directional freeze crystallization

NASA Technical Reports Server (NTRS)

Conlon, William M. (Inventor)

1996-01-01

A Directional Freeze Crystallization system employs an indirect contact heat exchanger to freeze a fraction of liquid to be purified. The unfrozen fraction is drained away and the purified frozen fraction is melted. The heat exchanger must be designed in accordance with a Growth Habit Index to achieve efficient separation of contaminants. If gases are dissolved in the liquid, the system must be pressurized.

The strength and dislocation microstructure evolution in superalloy microcrystals

NASA Astrophysics Data System (ADS)

Hussein, Ahmed M.; Rao, Satish I.; Uchic, Michael D.; Parthasarathay, Triplicane A.; El-Awady, Jaafar A.

2017-02-01

In this work, the evolution of the dislocations microstructure in single crystal two-phase superalloy microcrystals under monotonic loading has been studied using the three-dimensional discrete dislocation dynamics (DDD) method. The DDD framework has been extended to properly handle the collective behavior of dislocations and their interactions with large collections of arbitrary shaped precipitates. Few constraints are imposed on the initial distribution of the dislocations or the precipitates, and the extended DDD framework can support experimentally-obtained precipitate geometries. Full tracking of the creation and destruction of anti-phase boundaries (APB) is accounted for. The effects of the precipitate volume fraction, APB energy, precipitate size, and crystal size on the deformation of superalloy microcrystals have been quantified. Correlations between the precipitate microstructure and the dominant deformation features, such as dislocation looping versus precipitate shearing, are also discussed. It is shown that the mechanical strength is independent of the crystal size, increases linearly with increasing the volume fraction, follows a near square-root relationship with the APB energy and an inverse square-root relationship with the precipitate size. Finally, the flow strength in simulations having initial dislocation pair sources show a flow strength that is about one half of that predicted from simulations starting with single dislocation sources. The method developed can be used, with minimal extensions, to simulate dislocation microstructure evolution in general multiphase materials.

SilMush: A procedure for modeling of the geochemical evolution of silicic magmas and granitic rocks

NASA Astrophysics Data System (ADS)

Hertogen, Jan; Mareels, Joyce

2016-07-01

A boundary layer crystallization modeling program is presented that specifically addresses the chemical fractionation in silicic magma systems and the solidification of plutonic bodies. The model is a Langmuir (1989) type approach and does not invoke crystal settling in high-viscosity silicic melts. The primary aim is to model a granitic rock as a congealed crystal-liquid mush, and to integrate major element and trace element modeling. The procedure allows for some exploratory investigation of the exsolution of H2O-fluids and of the fluid/melt partitioning of trace elements. The procedure is implemented as a collection of subroutines for the MS Excel spreadsheet environment and is coded in the Visual Basic for Applications (VBA) language. To increase the flexibility of the modeling, the procedure is based on discrete numeric process simulation rather than on solution of continuous differential equations. The program is applied to a study of the geochemical variation within and among three granitic units (Senones, Natzwiller, Kagenfels) from the Variscan Northern Vosges Massif, France. The three units cover the compositional range from monzogranite, over syenogranite to alkali-feldspar granite. An extensive set of new major element and trace element data is presented. Special attention is paid to the essential role of accessory minerals in the fractionation of the Rare Earth Elements. The crystallization model is able to reproduce the essential major and trace element variation trends in the data sets of the three separate granitic plutons. The Kagenfels alkali-feldspar leucogranite couples very limited variation in major element composition to a considerable and complex variation of trace elements. The modeling results can serve as a guide for the reconstruction of the emplacement sequence of petrographically distinct units. Although the modeling procedure essentially deals with geochemical fractionation within a single pluton, the modeling results bring up a number of questions about the petrogenetic relationships among parental magmas of nearly coeval granitic units emplaced in close proximity.

Constraints on the depth of generation and emplacement of a magmatic epidote-bearing quartz diorite pluton in the Coast Plutonic Complex, British Columbia

USGS Publications Warehouse

Chang, J.M.; Andronicos, C.L.

2009-01-01

Petrology and P-T estimates indicate that a magmatic epidote-bearing quartz diorite pluton from Mt. Gamsby, Coast Plutonic Complex, British Columbia, was sourced at pressures below ???1.4 GPa and cooled nearly isobarically at ???0.9 GPa. The P-T path indicates that the magma was within the stability field of magmatic epidote early and remained there upon final crystallization. The pluton formed and crystallized at depths greater than ???30 km. REE data indicate that garnet was absent in the melting region and did not fractionate during crystallization. This suggests that the crust was less than or equal to ???55 km thick at 188 Ma during the early phases of magmatism in the Coast Plutonic Complex. Late Cretaceous contractional deformation and early Tertiary extension exhumed the rocks to upper crustal levels. Textures of magmatic epidote and other magmatic phases, combined with REE data, can be important for constraining the P-T path followed by magmas. ?? 2009 Blackwell Publishing Ltd.

A layer of neutrally buoyant olivine in the early stages of a deep lunar magma ocean and a possible consecutive overturn

NASA Astrophysics Data System (ADS)

Krättli, G.; Schmidt, M. W.

2017-12-01

The moon is thought to have undergone a completely molten stage during its accretion, the lunar magma ocean. In order to understand the evolution and first differentiation of the lunar magma ocean, we performed a series of consecutive liquidus experiments at pressures of the lower half of the lunar magma ocean. In these experiments, we determined the liquidus, crystallized some amount of minerals (typically 10-20%) and then stepped to a new bulk composition representing the residual liquid after fractionation of these minerals. Mineral and melt densities were then calculated in order to decide whether minerals would float or sink. The bulk lunar composition used in this study (Taylor 1982) results in extensive early olivine crystallization with high XMg (94-90) for all experimental pressures, the liquidus temperature slightly decreasing from 1900 to 1850°C from 4.5 to 3.5 GPa. Crystallization begins at the core-mantle boundary, but calculations indicate that olivine initially floats and becomes neutrally buoyant at 3.5-3.7 GPa, leading to a stable olivine layer of several 100 km thickness at this depth. This layer should rapidly compact yielding two chemically separated magma reservoirs. Olivine crystallization is followed by orthopyroxene (1650°C, twm_fr2), minor garnet (1600°C, twm_fr3), clinopyroxene and spinel (1550°C, twm_fr3) in the lower magma ocean. Despite continuously decreasing XMg and increasing Ca/Al, further experiments indicate that the more extensively fractionated lower magma should become finally buoyant, possibly causing an overturn of the previously layered structure. Additionally, few centrifuge assisted experiments at 2.5-3.5 GPa were performed showing decreasing olivine-melt density contrasts with increasing pressure. Slightly higher pressures would be necessary to positively prove the neutral buoyancy of olivine at 3.6 GPa, currently we are improving the piston cylinder on the centrifuge to reach 4 GPa. Taylor, Stuart Ross. Planetary science: a lunar perspective. Vol. 3303. Houston: Lunar and Planetary Institute, 1982.

NMR signal analysis to attribute the components to the solid/liquid phases present in mixes and ice creams.

PubMed

Mariette, François; Lucas, Tiphaine

2005-03-09

The NMR relaxation signals from complex products such as ice cream are hard to interpret because of the multiexponential behavior of the relaxation signal and the difficulty of attributing the NMR relaxation components to specific molecule fractions. An attribution of the NMR relaxation parameters is proposed, however, based on an approach that combines quantitative analysis of the spin-spin and spin-lattice relaxation times and the signal intensities with characterization of the ice cream components. We have been able to show that NMR can be used to describe the crystallized and liquid phases separately. The first component of the spin-spin and spin-lattice relaxation describes the behavior of the protons of the crystallized fat in the mix. The amount of fat crystals can then be estimated. In the case of ice cream, only the spin-lattice relaxation signal from the crystallized fraction is relevant. However, it enables the ice protons and the protons of the crystallized fat to be distinguished. The spin-lattice relaxation time can be used to describe the mobility of the protons in the different crystallized phases and also to quantify the amount of ice crystals and fat crystals in the ice cream. The NMR relaxation of the liquid phase of the mix has a biexponential behavior. A first component is attributable to the liquid fraction of the fat and to the sugars, while a second component is attributable to the aqueous phase. Overall, the study shows that despite the complexity of the NMR signal from ice cream, a number of relevant parameters can be extracted to study the influence of the formulation and of the process stages on the ice fraction, the crystallized fat fraction, and the liquid aqueous fraction.

The petrogenesis of late Neoproterozoic mafic dyke-like intrusion in south Sinai, Egypt

NASA Astrophysics Data System (ADS)

Azer, M. K.; Abu El-Ela, F. F.; Ren, M.

2012-08-01

New field, petrographical and geochemical studies are presented here for the late Neoproterozoic Rimm intrusion (˜15 km long) exposed in the southern Sinai Peninsula, Egypt in the northernmost Arabian-Nubian Shield (ANS). Field relations indicate that the Rimm intrusion is younger than the surrounding metamorphic rocks and calc-alkaline syn-tectonic granodiorite and it was not affected by regional metamorphism. The anorogenic peralkaline granite of Gebel Serbal crosscuts the Rimm intrusion. The Rimm intrusion is made up of several consanguineous rock types with gradational contacts. It is composed chiefly of pyroxene-hornblende gabbro, hornblende gabbro and minor quartz diorite. The chemical composition of the mafic minerals indicated that the studied rocks derived from calc-alkaline mafic magma. Geochemically, the studied rocks are characterized by enrichment in LILE relative to HFSE and LREE relative to HREE [(Ce/Yb)N = 4.50-6.36]. Quartz diorite display slightly concave HREE pattern and slightly negative Eu-anomaly [(Eu/Eu*)n = 0.91] which may be the result of fractionation of amphibole and plagioclase from the source melt, respectively. The Rimm intrusion evolved from mafic mantle magma into different type rocks by fractional crystallization with minor crustal contamination. The initial magma corresponds to pyroxene-hornblende gabbro and the crystallization of hornblende was caused by slight H2O increase in magma after crystallization of near-liquidus clinopyroxene and Ca-rich plagioclase. Amphiboles geobarometer indicate that the gabbroic rocks of the Rimm intrusion crystallized at pressures between 4.8 and 6.4 Kb, while quartz diorite crystallized at 1.3-2.1 Kb. Crystallization temperatures range between 800 and 926 °C for the gabbros and between 667 and 784 °C for the quartz diorite. The Rimm intrusion represents a post-orogenic phase formed during the crustal thinning and extension of the Arabian-Nubian Shield.

Assimilation of granite by basaltic magma at Burnt Lava flow, Medicine Lake volcano, northern California: Decoupling of heat and mass transfer

USGS Publications Warehouse

Grove, T.L.; Kinzler, R.J.; Baker, M.B.; Donnelly-Nolan, J. M.; Lesher, C.E.

1988-01-01

At Medicine Lake volcano, California, andesite of the Holocene Burnt Lava flow has been produced by fractional crystallization of parental high alumina basalt (HAB) accompanied by assimilation of granitic crustal material. Burnt Lava contains inclusions of quenched HAB liquid, a potential parent magma of the andesite, highly melted granitic crustal xenoliths, and xenocryst assemblages which provide a record of the fractional crystallization and crustal assimilation process. Samples of granitic crustal material occur as xenoliths in other Holocene and Pleistocene lavas, and these xenoliths are used to constrain geochemical models of the assimilation process. A large amount of assimilation accompanied fractional crystallization to produce the contaminated Burnt lava andesites. Models which assume that assimilation and fractionation occurred simultaneously estimate the ratio of assimilation to fractional crystallization (R) to be >1 and best fits to all geochemical data are at an R value of 1.35 at F=0.68. Petrologic evidence, however, indicates that the assimilation process did not involve continuous addition of granitic crust as fractionation occurred. Instead, heat and mass transfer were separated in space and time. During the assimilation process, HAB magma underwent large amounts of fractional crystallization which was not accompanied by significant amounts of assimilation. This fractionation process supplied heat to melt granitic crust. The models proposed to explain the contamination process involve fractionation, replenishment by parental HAB, and mixing of evolved and parental magmas with melted granitic crust. ?? 1988 Springer-Verlag.

Non-Newtonian behavior of plagioclase-bearing basaltic magma: Subliquidus viscosity measurement of the 1707 basalt of Fuji volcano, Japan

NASA Astrophysics Data System (ADS)

Ishibashi, Hidemi

2009-03-01

Laboratory measurements of viscosity were done for basalt erupted in 1707 AD from Fuji volcano, Japan, using a concentric cylinder rotational viscometer at temperatures of 1297-1157 °C, 1 atm pressure, and fO 2 near the Ni-NiO buffer. On cooling, elongated plagioclase crystals with a mean length/width ratio of ca. 8.5 appeared at 1237 °C, followed by olivine at 1157 °C. At progressively lower temperatures, the total crystal volume fraction increased monotonously to ca. 0.25; viscosity increased from 38.9 to 765 Pa s at a shear strain rate of 1 s - 1 . This basalt magma behaves as a Newtonian fluid at temperatures greater than 1217 °C, but shear-thinning behavior occurs at temperatures less than 1197 °C because of the suspended plagioclase crystals. This behavior is well approximated as a power law fluid. At the onset of shear thinning, the crystal volume fraction was between 0.06 and 0.13, which is attributed to the pronounced lath-shape of plagioclase crystals. The relative viscosity increases monotonously with increase of crystal volume fraction at a constant shear strain rate, and with decrease of shear strain rate at a constant crystal volume fraction. A modified form of the Krieger-Dougherty equation is introduced herein. It enables us to describe the dependencies of relative viscosity on both the crystal volume fraction and shear strain rate, and consequently the onset of shear-thinning behavior.

Timescale of Petrogenetic Processes Recorded in the Mount Perkins Magma System, Northern Colorado River Extension Corridor, Arizona

NASA Technical Reports Server (NTRS)

Danielson, Lisa R.; Metcalf, Rodney V.; Miller, Calvin F.; Rhodes Gregory T.; Wooden, J. L.

2013-01-01

The Miocene Mt. Perkins Pluton is a small composite intrusive body emplaced in the shallow crust as four separate phases during the earliest stages of crustal extension. Phase 1 (oldest) consists of isotropic hornblende gabbro and a layered cumulate sequence. Phase 2 consists of quartz monzonite to quartz monzodiorite hosting mafic microgranitoid enclaves. Phase 3 is composed of quartz monzonite and is subdivided into mafic enclave-rich zones and enclave-free zones. Phase 4 consists of aphanitic dikes of mafic, intermediate and felsic compositions hosting mafic enclaves. Phases 2-4 enclaves record significant isotopic disequilibrium with surrounding granitoid host rocks, but collectively enclaves and host rocks form a cogenetic suite exhibiting systematic variations in Nd-Sr-Pb isotopes that correlate with major and trace elements. Phases 2-4 record multiple episodes of magma mingling among cogenetic hybrid magmas that formed via magma mixing and fractional crystallization at a deeper crustal. The mafic end-member was alkali basalt similar to nearby 6-4 Ma basalt with enriched OIB-like trace elements and Nd-Sr-Pb isotopes. The felsic end-member was a subalkaline crustal-derived magma. Phase 1 isotropic gabbro exhibits elemental and isotopic compositional variations at relatively constant SiO2, suggesting generation of isotropic gabbro by an open-system process involving two mafic end-members. One end-member is similar in composition to the OIB-like mafic end-member for phases 2-4; the second is similar to nearby 11-8 Ma tholeiite basalt exhibiting low epsilon (sub Nd), and depleted incompatible trace elements. Phase 1 cumulates record in situ fractional crystallization of an OIB-like mafic magma with isotopic evidence of crustal contamination by partial melts generated in adjacent Proterozoic gneiss. The Mt Perkins pluton records a complex history in a lithospheric scale magma system involving two distinct mantle-derived mafic magmas and felsic magma sourced in the crust. Mixing and fractional crystallization of these magmas at various levels in the crust generated a suite of intermediate composition magmas. U-Pb zircon SHRIMP ages of phase 1 (15.7 +/- 0.2 Ma), phase 3 (15.8 +/- 0.2 Ma) and phase 4 (15.4 +/- 0.3 Ma) document a 100-300k year timescale for petrogenetic processes recorded in the Mt Perkins magma system.

Oxygen isotope trajectories of crystallizing melts: Insights from modeling and the plutonic record

NASA Astrophysics Data System (ADS)

Bucholz, Claire E.; Jagoutz, Oliver; VanTongeren, Jill A.; Setera, Jacob; Wang, Zhengrong

2017-06-01

Elevated oxygen isotope values in igneous rocks are often used to fingerprint supracrustal alteration or assimilation of material that once resided near the surface of the earth. The δ18O value of a melt, however, can also increase through closed-system fractional crystallization. In order to quantify the change in melt δ18O due to crystallization, we develop a detailed closed-system fractional crystallization mass balance model and apply it to six experimentally- and naturally-determined liquid lines of descent (LLDs), which cover nearly complete crystallization intervals (melt fractions of 1 to <0.1). The studied LLDs vary from anhydrous tholeiitic basalts to hydrous high-K and calc-alkaline basalts and are characterized by distinct melt temperature-SiO2 trajectories, as well as, crystallizing phase relationships. Our model results demonstrate that melt fraction-temperature-SiO2 relationships of crystallizing melts, which are strongly a function of magmatic water content, will control the specific δ18O path of a crystallizing melt. Hydrous melts, typical of subduction zones, undergo larger increases in δ18O during early stages of crystallization due to their lower magmatic temperatures, greater initial increases in SiO2 content, and high temperature stability of low δ18O phases, such as oxides, amphibole, and anorthitic plagioclase (versus albite). Conversely, relatively dry, tholeiitic melts only experience significant increases in δ18O at degrees of crystallization greater than 80%. Total calculated increases in melt δ18O of 1.0-1.5‰ can be attributed to crystallization from ∼50 to 70 wt.% SiO2 for modeled closed-system crystallizing melt compositions. As an example application, we compare our closed system model results to oxygen isotope mineral data from two natural plutonic sequences, a relatively dry, tholeiitic sequence from the Upper and Upper Main Zones (UUMZ) of the Bushveld Complex (South Africa) and a high-K, hydrous sequence from the arc-related Dariv Igneous Complex (Mongolia). These two sequences were chosen as their major and trace element compositions appear to have been predominantly controlled by closed-system fractional crystallization and their LLDs have been modeled in detail. We calculated equilibrium melt δ18O values using the measured mineral δ18O values and calculated mineral-melt fractionation factors. Increases of 2-3‰ and 1-1.5‰ in the equilibrium melts are observed for the Dariv Igneous Complex and the UUMZ of the Bushveld Complex, respectively. Closed-system fractional crystallization model results reproduce the 1‰ increase observed in the equilibrium melt δ18O for the Bushveld UUMZ, whereas for the Dariv Igneous Complex assimilation of high δ18O material is necessary to account for the increase in melt δ18O values. Assimilation of evolved supracrustal material is also confirmed with Sr and Nd isotope analyses of clinopyroxene from the sequence. Beginning with a range of mantle-derived basalt δ18O values of 5.7‰ ("pristine" mantle) to ∼7.0‰ (heavily subduction-influenced mantle), our model results demonstrated that high-silica melts (i.e. granites) with δ18O of up to 8.5‰ can be produced through fractional crystallization alone. Lastly, we model the zircon-melt δ18O fractionations of different LLDs, emphasizing their dependence on the specific SiO2-T relationships of a given crystallizing melt. Wet, relatively cool granitic melts will have larger zircon-melt fractionations, potentially by ∼1.5‰, compared to hot, dry granites. Therefore, it is critical to constrain zircon-melt fractionations specific to a system of interest when using zircon δ18O values to calculate melt δ18O.

Fractional Crystallisation of Archaean Trondhjemite Magma at 12-7 Kbar: Constraints on Rheology of Archaean Continental Crust

NASA Astrophysics Data System (ADS)

Sarkar, Saheli; Saha, Lopamudra; Satyanarayan, Manavalan; Pati, Jayanta

2015-04-01

Fractional Crystallisation of Archaean Trondhjemite Magma at 12-7 Kbar: Constraints on Rheology of Archaean Continental Crust Sarkar, S.1, Saha, L.1, Satyanarayan, M2. and Pati, J.K.3 1. Department of Earth Sciences, Indian Institute of Technology Roorkee, Roorkee-247667, Haridwar, India, 2. HR-ICPMS Lab, Geochemistry Group, CSIR-National Geophysical Research Institute, Hyderabad-50007, India. 3. Department of Earth and Planetary Sciences, Nehru Science Centre, University of Allahabad, Allahabad-211002, India. Tonalite-Trondhjemite-Granodiorite (TTGs) group of rocks, that mostly constitute the Archaean continental crusts, evolved through a time period of ~3.8 Ga-2.7 Ga with major episodes of juvenile magma generations at ~3.6 Ga and ~2.7 Ga. Geochemical signatures, especially HREE depletions of most TTGs conform to formation of this type of magma by partial melting of amphibolites or eclogites at 15-20 kbar pressure. While TTGs (mostly sodic in compositions) dominates the Eoarchaean (~3.8-3.6 Ga) to Mesoarchaean (~3.2-3.0 Ga) domains, granitic rocks (with significantly high potassium contents) became more dominant in the Neoarchaean period. The most commonly accepted model proposed for the formation of the potassic granite in the Neoarchaean time is by partial melting of TTGs along subduction zones. However Archaean granite intrusive into the gabbro-ultramafic complex from Scourie, NW Scotland has been interpreted to have formed by fractional crystallization of hornblende and plagioclase from co-existing trondhjemitic gneiss. In this study we have studied fractional crystallization paths from a Mesoarchaean trondhjemite from the central Bundelkhand craton, India using MELTS algorithm. Fractional crystallization modeling has been performed at pressure ranges of 20 kbar to 7 kbar. Calculations have shown crystallization of garnet-clinopyroxene bearing assemblages with progressive cooling of the magma at 20 kbar. At pressure ranges 19-16 kbar, solid phases fractionating from the magma are mostly clinopyroxene with minor orthopyroxene. Plagioclase crystals appear at pressures ≤ 15 kbar. Plagioclase crystals are mostly albitic in composition (XAb ~0.70-0.75). At each pressure, with progressive cooling and fractionation of solid phases, crystal-melt ratio becomes significantly higher, magma becomes more depleted in Al2O3, MgO, with significant increase in K2O/Na2O ratio and water content. With progressive cooling and fractionation, overall composition of the magma changes from trondhjemitic to granitic, with increase in viscosity from 4.5 poise to 5.5 poise. The study thus reveals that fractional crystallization of trondhemitic magmas at different depths can form more potassic granitic magma with higher viscosity. As Hf isotope signatures from most Archaean TTGs reveal longer crustal residence, it is likely that granitic magmas that became more common in the Neoarchaean period, could also possibly been derived by fractional crystallization from trondhjemitic magmas in Mesoarchaean time. Granitic magmas hence generated have much higher viscosity compared to the parent trondhjemitic magma. Low viscosity of trondhjemitic magmas and low crystal-melt ratios in the initial stages of crystallization (as derived in this study), may be the cause of formation of large bodies of TTGs in Early Archaean period. Close to Neoarchaean period more granitic magmas are observed. In this study it has been observed that crystallization of these magmas lead to high crystal-melt ratios and the magmas have higher viscosity. Such change in composition from Early to Neoarchaean time must have made Archaean crusts stronger and hence more prone to deformation. This observation hence support occurrence of Phanerozoic style signatures from poly-deformed terrains of Neoarchaean time.

Geochemistry of carbonatites of the Tomtor massif

USGS Publications Warehouse

Kravchenko, S.M.; Czamanske, G.; Fedorenko, V.A.

2003-01-01

Carbonatites compose sheet bodies in a 300-m sequence of volcanic lamproites, as well as separate large bodies at depths of >250-300 m. An analysis of new high-precision data on concentrations of major, rare, and rare earth elements in carbonatites shows that these rocks were formed during crystallization differentiation of a carbonatite magma, which resulted in enrichment of the later melt fractions in rare elements and was followed by autometasomatic and allometasomatic hydrothermal processes. Some independent data indicate that the main factor of ore accumulation in the weathered rock zone (also known as the "lower ore horizon" comprising metasomatized volcanics with interbedded carbonatites) was hydrothermal addition of Nb and REEs. The giant size of the Tomtor carbonatite-nepheline syenite massif caused advanced magma differentiation, extensive postmagmatic metasomatism and recrystallization of host rocks, and strong enrichment of carbonatites in incompatible rare and rare earth elements (except for Ta, Zr, Ti, K, and Rb) compared to the rocks of many other carbonatite massifs. We suggest that a wide range of iron contents in carbonatites-2 can be related to extensive magnetite fractionation at the magmatic stage in different parts of the huge massif. Copyright ?? 2003 by MAIK "Nauka/Interperiodica" (Russia).

Magnetic and electric control of multiferroic properties in monodomain crystals of BiFeO3

NASA Astrophysics Data System (ADS)

Tokunaga, Masashi

One of the important goals for multiferroics is to develop the non-volatile magnetic memories that can be controlled by electric fields with low power consumption. Among numbers of multiferroic materials, BiFeO3 has been the most extensively studied because of its substantial ferroelectric polarization and magnetic order up to above room temperature. Recent high field experiments on monodomain crystals of BiFeO3 revealed the existence of additional electric polarization normal to the three-fold rotational axis. This transverse component is coupled with the cycloidal magnetic domain, and hence, can be controlled by external magnetic fields. Application of electric fields normal to the trigonal axis modifies volume fraction of these multiferroic domains, which involves change in resistance of the sample, namely exhibits the bipolar resistive memory effect. In this talk, I will introduce the effects of magnetic and electric fields on magnetoelectric and structural properties observed in monodomain crystals of BiFeO3. This work was supported by JSPS Grant Number 16K05413 and by a research Grant from The Murata Science Foundation.

Competition between crystallization and vitrification of the rigid amorphous fraction in poly(3-hydroxybutyrate)

NASA Astrophysics Data System (ADS)

Di Lorenzo, Maria Laura; Righetti, Maria Cristina; Gazzano, Massimo

2012-07-01

Semicrystalline polymers have a metastable nanophase structure, where the various nanophases can be crystal, liquid, glass, or mesophase. This multi-level structure is determined by a competition among self-organization, crystallization, and vitrification of the amorphous segments and is established during material processing. The kinetics of such competition is here determined for poly(3-hydroxybutyrate) (PHB), as vitrification/devitrification of the rigid amorphous fraction strongly affects crystallization kinetics of PHB.

Shallow fractionation signature of phase chemistry in Taburiente lavas, La Palma, Canary Islands: Results of MELTS modeling

NASA Astrophysics Data System (ADS)

Guetschow, H. A.; Nelson, B. K.

2002-12-01

Depth of crystal fractionation influences the chemical evolution of ocean island basalts and has significant implications for the physical structures of these volcanoes. In contrast to dominantly shallow systems such as Hawaii, a range of fractionation depths have been reported for Canary Islands lavas. Magmas erupted on La Palma preserve fluid- and melt-inclusion evidence for high-pressure (> 10 kbar) crystallization (Klügel et al., 1998; Hansteen et al., 1998; Nikogosian et al., 2002). If high-pressure fractional crystallization were an early and dominant process, it would generate specific patterns in rock and phase chemistry of eruptive sequences. Alkalic basalts from Taburiente volcano display coherent major element trends consistent with evolution dominated by fractional crystallization while their phenocryst compositions, trace elements, and isotopic trends require mixing between multiple sources. The current model confirms the importance of both fractionation and mixing to achieve the full range of lavas observed. A low-pressure (1 kbar) thermodynamic fractional crystallization model performed with the MELTS (Ghiorso and Sack, 1995) software closely reproduces major element trends from two stratigraphic sequences. This model also predicts the observed sequence of groundmass clinopyroxene compositions and phenocryst zoning reversals. In all low pressure simulations, olivine remains a modally significant liquidus phase during the first 20% and last 30% of the crystallization sequence, resulting in a negative correlation between the CaO and Fo content of olivine. These results are consistent with the presence of olivine phenocrysts that bear petrographic evidence of early crystallization, as well as observed compositional trends of groundmass olivine and clinopyroxene in Taburiente lavas. MELTS models that include an initial period of high pressure (12 kbar) clinopyroxene fractionation produce major element trends comparable to the low pressure model, but also produce high modal volumes of low CaO, high MgO clinopyroxene that are not observed in sections we studied. Removal of such a large quantity of clinopyroxene from the liquid increases the TiO2 and CaO of later-crystallized clinopyroxene to concentrations not observed in our studied sections, and restricts the MgO and FeO* to smaller ranges than observed. Olivine fractionation is restricted to short duration and low abundance late in the crystallization sequence, which is not evident petrographically. The total compositional range of clinopyroxene and olivine crystals observed throughout this suite of rocks is larger than any generated by a single-source MELTS model. Combined with stratigraphically controlled Pb isotope variations it indicates magma mixing and fractionation at low pressures dominates the petrologic diversity in these sections. Hansteen, TH, Klügel, A., Schmincke, H.-U, 1998. Contrib. Min. Pet. 132, 48-64. Klügel, A, 1998. Contrib. Min. Pet. 131, 237-257. Nikogosian, IK, Elliott, T, Touret, JLR. 2002. Chem. Geo. 183, 169-193. Ghiorso, MS, and Sack, RO. Contrib. Min. Pet. 119, 197-212.

Fractional Wigner Crystal in the Helical Luttinger Liquid.

PubMed

Traverso Ziani, N; Crépin, F; Trauzettel, B

2015-11-13

The properties of the strongly interacting edge states of two dimensional topological insulators in the presence of two-particle backscattering are investigated. We find an anomalous behavior of the density-density correlation functions, which show oscillations that are neither of Friedel nor of Wigner type: they, instead, represent a Wigner crystal of fermions of fractional charge e/2, with e the electron charge. By studying the Fermi operator, we demonstrate that the state characterized by such fractional oscillations still bears the signatures of spin-momentum locking. Finally, we compare the spin-spin correlation functions and the density-density correlation functions to argue that the fractional Wigner crystal is characterized by a nontrivial spin texture.

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

De Yoreo, J; Orme, C; Dove, P

Since the dawn of life on earth, organisms have directed the crystallization of inorganic ions from solution to form minerals that meet specific biological needs. The resulting materials often exhibit remarkable properties, making the processes involved in biomineralization of interest to a wide array of scientific disciplines. From a geochemical standpoint, perhaps the most important consequence is that CaCO{sub 3} biomineral formation occurs in the Oceans on such a large scale that it influences many aspects of seawater chemistry and results in sequestration of carbon in the form of carbonate sediments. In this manner, the products of biomineralization are preservedmore » in the rock record and serve as an extensive chronicle of the interplay between biota and the earth system environment. From the point of view of materials synthesis, biological control over epitaxy is an elegant example of self-organization in complex molecular systems. Through selective introduction of peptides and proteins, living organisms deterministically modify nucleation, step kinetics, surface morphologies, and facet stabilities to produce nanophase materials, topologically complex single-crystals, and multi-layer composite. The resulting materials have biological functions as diverse as structural supports, porous filtration media, grinding and cutting tools, lenses, gravity sensors and magnetic guidance systems. As Table I shows, calcium carbonate minerals are ubiquitous amongst these biomineral structures. In addition , calcium carbonate is a well studied material that is easily crystallized and has known solution chemistry. Consequently, the calcium carbonate system provides an excellent model for investigating biomineralization processes. Surprisingly, in spite of the identification of carbonate biogenesis as a critical contributor to the carbon reservoir mediating climate change, and the enormous potential of biomimetic synthesis for production of tailored, crystalline nano- and micro-structured materials, the fundamental physical controls on carbonate biomineral formation remain poorly understood. Carbonates are formed in diverse environments almost exclusively by living organisms. These naturally occurring marine and fresh water minerals most commonly occur as the polymorphs of calcite, aragonite and vaterite which are nucleated and grown in the exoskeletons and tissues of marine and freshwater organisms ranging from simple bacteria and algae to crustaceans, molluscs, or sponges. It is known that the soluble fraction associated with mineralizing parts of organisms plays a primary role in crystal formation. In the formation of molluscan shells, this fraction is distinguished by the common presence of aspartic acid rich amino acid mixtures. It is also known that carbonates exposed to different polyamino acids exhibit different crystal habits. Belcher et al. showed that exposing growing CaCO{sub 3} crystals alternately to solutions containing polyanionic proteins associated with the aragonitic and calcitic layers of mollusc shells led to sequential switching of the crystal structure of the newly grown material between that of aragonite and calcite. Further work has demonstrated that these protein mixtures alter the morphology of the calcite growth surface and that they contain two fractions effecting growth: a step-binding fraction that inhibits step advancement on calcite surfaces, and a surface binding fraction that appears to lead to the subsequent nucleation of aragonite. Wierzbicki et al. found that polyaspartate molecules (ASP{sub 20}) bind to calcite surfaces. Finally, modeling of ASP{sub 15} binding to calcite planes predicts large binding energies for well defined orientations. This and related evidence shows that systematic relationships between crystal morphology and surface interactions with the reactive groups of the organic molecules must exist. However, the interplay between surface chemistry and the physical processes of nucleation and crystal growth are poorly understood because, until recently only ex situ biochemical studies focusing on the effect of changes in solution chemistry and/or surface stereo-chemistry on macroscopic crystal morphology had been performed.« less

Polymorphic Transformation in Mixtures of High- and Low-Melting Fractions of Milk Fat

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

Cisneros,A.; Mazzanti, G.; Campos, R.

2006-01-01

The kinetics of crystallization of high-melting fraction (HMF) and a mixture of 40% HMF and 60% low-melting fraction (LMF) of milk fat were studied at 5 C by time-resolved in-situ synchrotron X-ray diffraction. HMF crystallized in the {alpha} polymorph, had a longer lifetime than the ones previously reported in pure milk fat, and was almost completely solid. The HMF/LMF mixture crystallized initially in the {alpha} form and transformed into the {beta}' polymorph, with a solid fat content much lower than that of HMF. The polymorphic change was therefore attributed to a delayed sudden formation of {beta}' mixed crystals from themore » uncrystallized melt. These findings are important for the food industry and as fundamental knowledge to improve our understanding of the origin of the macroscopic physical properties of solid milk fat fractions used in many manufacturing processes.« less

Lattice Boltzmann Simulation of Kinetic Isotope Effect During Snow Crystal Formation

NASA Astrophysics Data System (ADS)

Lu, G.; Depaolo, D. J.; Kang, Q.; Zhang, D.

2007-12-01

The isotopic composition of precipitation, especially that of snow, plays a special role in the global hydrological cycle and in reconstruction of past climates using polar ice cores. The fractionation of the major water isotope species (HHO, HDO, HHO-18) during ice crystal formation is critical to understanding the global distribution of isotopes in precipitation. Ice crystal growth in clouds is traditionally treated with a spherically-symmetric steady state diffusion model, with semi-empirical modifications added to account for ventilation and for complex crystal morphology. Although it is known that crystal growth rate, which depends largely on the degree of vapor over- saturation, determines crystal morphology, there are no quantitative models that relate morphology to the vapor saturation factor. Since kinetic (vapor phase diffusion-controlled) isotopic fractionation also depends on growth rate, there should be direct relationships between vapor saturation, crystal morphology, and crystal isotopic composition. We use a 2D lattice Boltzmann model to simulate diffusion-controlled ice crystal growth from vapor- oversaturated air. In the model, crystals grow solely according to the diffusive fluxes just above the crystal surfaces, and hence crystal morphology arises from the initial and boundary conditions in the model and does not need to be specified a priori. Crystal growth patterns can be varied between random growth and deterministic growth (along the maximum concentration gradient for example). The input parameters needed are the isotope- dependent vapor deposition rate constant (k) and the water vapor diffusivity in air (D). The values of both k and D can be computed from kinetic theory, and there are also experimentally determined values of D. The deduced values of k are uncertain to the extent that the condensation coefficient for ice is uncertain. The ratio D/k is a length (order 1 micron) that determines the minimum scale of dendritic growth features and allows us to scale the numerical calculations to atmospheric conditions. Our calculations confirm that the crystal/vapor isotopic fractionation approaches the equilibrium value, and the crystals are compact (circular in 2D) as the saturation factor approaches unity (S= 1.0). However, few natural crystals form under such conditions. At higher oversaturation (e.g. S = 1.2), dendritic crystals of millimeter size develop on timescales appropriate to cloud processes, and kinetic effects control isotopic fractionation. Fractionation factors for dendritic crystals are similar to those predicted by the spherical diffusion model, but the model also gives estimates of crystal heterogeneity. Dendritic crystals are constrained to be relatively large, with dimension much greater than about 20D/k. The most difficult aspect of the modeling is to account for the large density difference between air and ice, which requires us to use a fictitious higher density for the vapor-oversaturated air and scale the crystal growth time accordingly. An approach using a larger scale simulation and the domain decomposition method can provide a vapor flux for a nested smaller scale calculation. The results clarify the controls on crystal growth, and the relationships between saturation state, growth rate, crystal morphology and isotopic fractionation.

The Ackley City Batholith, southeastern Newfoundland: Evidence for crystal versus liquid-state fractionation

NASA Astrophysics Data System (ADS)

Whalen, J. B.

1983-08-01

The 345 ± 10 Ma old composite Ackley City Batholith of southeastern Newfoundland, consists largely of very felsic K-feldspar megacrystic granite and alaskite. Spatially related to the southeast contact of the alaskite are younger aplites and pegmatite, intrusive phases which are interpreted to be pan of a tilted, high level roof zone complex to the batholith. The compositions of the alaskite and roof zone complex define major and trace element gradients similar to those in voluminous high-silica eruptive suites; i.e., the alaskite is more chemically evolved (higher in Rb, lower in Ca, Fe, Mn, Ti, P, Sr, Ba and LREE) toward the roof. Apparently these chemical gradients in the batholith are restricted to the top 2 to 3 kms of the former magma chamber. Fractional crystallization is a plausible process for generating the chemical dispersion in the granites, although very high feldspar partition coefficients for Ba, Sr and Eu are required to generate the observed chemical gradients by a reasonable degree of fractional crystallization. Restriction of crystal fractionation to near the roof of the batholith may reflect a decreased viscosity which would facilitate crystal-liquid separation by processes such as filter pressing, flow differentiation or convective fractionation. The chemical gradients in these granites closely resemble those attributed in high-silica volcanics to the process of thermogravitational diffusion (TGD). Compositional gradients in the upper portion of a magma chamber are consistent with the TGD model. This model, although still poorly understood, is, like fractional crystallization, a plausible mechanism to generate the chemical features of the Ackley City granites.

Role of lattice distortion on diffuse phase transition temperatures in Bi0.5Na0.5TiO3-BaTiO3 [BNBTO] solid solutions

NASA Astrophysics Data System (ADS)

Pradhan, Lagen Kumar; Pandey, Rabichandra; Kumar, Sunil; Supriya, Sweety; Kar, Manoranjan

2018-04-01

Effect of lattice distortion on diffuse phase transition in BNBTO solid solutions near Morphotropic phase boundary (MPB) has been investigated. Solid solutions of (Bi0.5Na0.5)1-xBaxTiO3 (with mole % of x= 0.04, 0.05, 0.06, 0.07 and 0.08) were prepared by the planetary ball mill method in ethanol medium. Rietveld refinement technique with rhombohedral (R3c) and tetragonal (P4bm) crystal symmetry has been employed for structural as well as phase analysis of the solid solutions. Both rhombohedral and tetragonal lattice distortion (c/a) tends toward the pseudo-cubic crystal symmetry with the increase of mole fraction of Ba2+ near MPB (x= 6 mole %). Also, the average crystallite size and grain size decrease with increase of mole fraction of Ba2+ in BNT ceramic are due to larger ionic radius of Ba2+ and grain boundary pinning process in the solid solutions respectively. Additionally, depolarization temperature (Td) and maximum temperature (Tm) reduces due to the lattice distortion of both the phases in BNBTO solid solutions, which is explained extensively. Significant increase of dielectric constant has been observed near MPB composition (x=6%) in BNBTO solid solutions.

Origin and evolution of the Nakhla meteorite inferred from the Sm-Nd and U-Pb systematics and REE, Ba, Sr, Rb and K abundances

NASA Technical Reports Server (NTRS)

Nakamura, N.; Unruh, D. M.; Tatsumoto, M.; Hutchison, R.

1982-01-01

Analyses of whole rock and mineral separates from the Nakhla meteorite are carried out by means of Sm-Nd and U-Tn-Pb systematics and by determining their REE, Ba, Sr, Rb, and K concentrations. Results show that the Sm-Nd age of the meteorite is 1.26 + or - 0.7 b.y., while the high initial epsilon(Nd) value of +16 suggests that Nakhla was derived from a light REE-depleted, old planetary mantle source. A three-stage Sm-Nd evolution model is developed and used in combination with LIL element data and estimated partition coefficients in order to test partial melting and fractional crystallization models and to estimate LIL abundances in a possible Nakhla source. The calculations indicate that partial melting of the source followed by extensive fractional crystallization of the partial melt could account for the REE abundances in the Nakhla constituent minerals. It is concluded that the significantly younger age of Nakhla than the youngest lunar rock, the young differentiation age inferred from U-Th-Pb data, and the estimated LIL abundances suggest that this meteorite may have been derived from a relatively large, well-differentiated planetary body such as Mars.

Pretreatment of Hanford medium-curie wastes by fractional crystallization.

PubMed

Nassif, Laurent; Dumont, George; Alysouri, Hatem; Rousseau, Ronald W

2008-07-01

Acceleration of the schedule for decontamination of the Hanford site using bulk vitrification requires implementation of a pretreatment operation. Medium-curie waste must be separated into two fractions: one is to go to a waste treatment and immobilization plant and a second, which is low-activity waste, is to be processed by bulk vitrification. The work described here reports research on using fractional crystallization for that pretreatment. Sodium salts are crystallized by evaporation of water from solutions simulating those removed from single-shell tanks, while leaving cesium in solution. The crystalline products are then recovered and qualified as low-activity waste, which is suitable upon redissolution for processing by bulk vitrification. The experimental program used semibatch operation in which a feed solution was continuously added to maintain a constant level in the crystallizer while evaporating water. The slurry recovered at the end of a run was filtered to recover product crystals, which were then analyzed to determine their composition. The results demonstrated that targets on cesium separation from the solids, fractional recovery of sodium salts, and sulfate content of the recovered salts can be achieved by the process tested.

Crystal settling and crystal growth caused by Ostwald Ripening in a terrestrial magma ocean under rotation

NASA Astrophysics Data System (ADS)

Maas, C.; Moeller, A.; Hansen, U.

2013-12-01

About 4.5 billion years ago the earth was covered by a heavily convecting and rotating global magma ocean which was caused by an impact of a mars-sized impactor in a later stage of the earth's accretion. After the separation of metal and silicate (see A. Möller, U. Hansen (2013)) and the formation of the earth's core it began to crystallize. Small silicate crystals emerge and grow by Ostwald Ripening when the fluid is supersaturated. This process results in shrinking of small crystals and growing of large crystals on behalf of the smaller ones. This leads to an altering of the crystal settling time. One question which is still under great debate is whether fractional or equilibrium crystallization occurred in the magma ocean. Fractional crystallization means that different mineral fractions settle one after the other which would lead to a strongly differentiated mantle after solidification of the magma ocean. In contrast to that equilibrium crystallization would result in a well mixed mantle. Whether fractional or equilibrium crystallization occurred is for example important for the starting model of plate tectonics or the understanding of the mantle development until today. To study the change of crystal radius in a convecting and rotating magma ocean we employed a 3D numerical model. Due to the low viscosity and strong rotation the influence of rotation on the early magma Ocean cannot be neglected. In the model the crystals are able to influence each other and the fluid flow. They are able to grow, shrink, vanish and form and gravitational, Coriolis and drag forces due to the fluid act on them. In our present work we study the crystal settling depending on different rotation rates and rotation axes with two configurations. For the polar setting the rotation axis is parallel, at the equator it is perpendicular to gravity. Low rotation at the pole leads to a large fraction of suspended crystals. With increasing rotation the crystals settle and form a thick layer at the bottom of the magma ocean. At the equator we find three regimes (see A. Möller, U. Hansen (2013)) depending on the rotation strength. At low rotation a high fraction of silicate crystals settle at the bottom. At higher rotation the crystals form a thick layer in the bottom 1/3 of box. At high rotation all crystals are suspended and we observe a ribbon structure in the middle of the box. With a second model we investigate growing and shrinking of crystals by Ostwald Ripening and include formation and melting. In general we observe the same behaviour and regimes as described above, however due to Ostwald Ripening the evolution of crystal radius with time depends on the strength of rotation and on the orientation of the rotation axis. Very first results show that at the pole the growth of the silicate crystals is limited. The resulting small radius leads to a slow crystal settling. At the equator the crystals are able to grow larger than at the pole and therefore settle faster. This could lead to an asymmetrical crystallization of the magma ocean. In an extreme case due to the different settling times this could lead to a well mixed mantle at the pole whereas at the equator the mantle could be strongly differentiated after the solidification of the magma ocean.

Magma oceanography. II - Chemical evolution and crustal formation. [lunar crustal rock fractional crystallization model

NASA Technical Reports Server (NTRS)

Longhi, J.

1977-01-01

A description is presented of an empirical model of fractional crystallization which predicts that slightly modified versions of certain of the proposed whole moon compositions can reproduce the major-element chemistry and mineralogy of most of the primitive highland rocks through equilibrium and fractional crystallization processes combined with accumulation of crystals and trapping of residual liquids. These compositions contain sufficient Al to form a plagioclase-rich crust 60 km thick on top of a magma ocean that was initially no deeper than about 300 km. Implicit in the model are the assumptions that all cooling and crystallization take place at low pressure and that there are no compositional or thermal gradients in the liquid. Discussions of the cooling and crystallization of the proposed magma ocean show these assumptions to be disturbingly naive when applied to the ocean as a whole. However, the model need not be applied to the whole ocean, but only to layers of cooling liquid near the surface.

Terrestrial photovoltaic collector technology trends

NASA Technical Reports Server (NTRS)

Shimada, K.; Costogue, E.

1984-01-01

Following the path of space PV collector development in its early stages, terrestrial PV technologies based upon single-crystal silicon have matured rapidly. Currently, terrestrial PV cells with efficiencies approaching space cell efficiencies are being fabricated into modules at a fraction of the space PV module cost. New materials, including CuInSe2 and amorphous silicon, are being developed for lowering the cost, and multijunction materials for achieving higher efficiency. Large grid-interactive, tracking flat-plate power systems and concentrator PV systems totaling about 10 MW, are already in operation. Collector technology development both flat-plate and concentrator, will continue under an extensive government and private industry partnership.

Crystallization of aqueous inorganic-malonic acid particles: nucleation rates, dependence on size, and dependence on the ammonium-to-sulfate ratio.

PubMed

Parsons, Matthew T; Riffell, Jenna L; Bertram, Allan K

2006-07-06

Using an electrodynamic balance, we determined the relative humidity (RH) at which aqueous inorganic-malonic acid particles crystallized, with ammonium sulfate ((NH(4))(2)SO(4)), letovicite ((NH(4))(3)H(SO(4))(2)), or ammonium bisulfate (NH(4)HSO(4)) as the inorganic component. The results for (NH(4))(2)SO(4)-malonic acid particles and (NH(4))(3)H(SO(4))(2)-malonic acid particles show that malonic acid decreases the crystallization RH of the inorganic particles by less than 7% RH when the dry malonic acid mole fraction is less than 0.25. At a dry malonic acid mole fraction of about 0.5, the presence of malonic acid can decrease the crystallization RH of the inorganic particles by up to 35% RH. For the NH(4)HSO(4)-malonic acid particles, the presence of malonic acid does not significantly modify the crystallization RH of the inorganic particles for the entire range of dry malonic acid mole fractions studied; in all cases, either the particles did not crystallize or the crystallization RH was close to 0% RH. Size dependent measurements show that the crystallization RH of aqueous (NH(4))(2)SO(4) particles is not a strong function of particle volume. However, for aqueous (NH(4))(2)SO(4)-malonic acid particles (with dry malonic acid mole fraction = 0.36), the crystallization RH is a stronger function of particle volume, with the crystallization RH decreasing by 6 +/- 3% RH when the particle volume decreases by an order of magnitude. To our knowledge, these are the first size dependent measurements of the crystallization RH of atmospherically relevant inorganic-organic particles. These results suggest that for certain organic mole fractions the particle size and observation time need to be considered when extrapolating laboratory crystallization results to atmospheric scenarios. For aqueous (NH(4))(2)SO(4) particles, the homogeneous nucleation rate data are a strong function of RH, but for aqueous (NH(4))(2)SO(4)-malonic acid particles (with dry organic mole fraction = 0.36), the rates are not as dependent on RH. The homogeneous nucleation rates for aqueous (NH(4))(2)SO(4) particles were parametrized using classical nucleation theory, and from this analysis we determined that the interfacial surface tension between the crystalline ammonium sulfate critical nucleus and an aqueous ammonium sulfate solution is between 0.053 and 0.070 J m(-2).

Phase equilibrium modelling of granite magma petrogenesis: B. An evaluation of the magma compositions that result from fractional crystallization

NASA Astrophysics Data System (ADS)

Garcia-Arias, Marcos; Stevens, Gary

2017-04-01

Several fractional crystallization processes (flow segregation, gravitational settling, filter-pressing), as well as batch crystallization, have been investigated in this study using thermodynamic modelling (pseudosections) to test whether they are able to reproduce the compositional trends shown by S-type granites. Three starting compositions comprising a pure melt phase and variable amounts of entrained minerals (0, 20 and 40 wt.% of the total magma) have been used to study a wide range of likely S-type magma compositions. The evolution of these magmas was investigated from the segregation from their sources at 0.8 GPa until emplacement at 0.3 GPa in an adiabatic path, followed by isobaric cooling until the solidus was crossed, in a closed-system scenario. The modelled magmas and the fractionated mineral assemblages are compared to the S-type granites of the Peninsula pluton, Cape Granite Suite, South Africa, which have a composition very similar to most of the S-type granites. The adiabatic ascent of the magmas digests partially the entrained mineral assemblage of the magmas, but unless this entrained assemblage represents less than 1 wt.% of the original magma, part of the mineral fraction survives the ascent up to the chosen pressure of emplacement. At the level of emplacement, batch crystallization produces magmas that only plot within the composition of the granites of the Peninsula pluton if the bulk composition of the original magmas already matched that of the granites. Flow segregation of crystals during the ascent and gravitational settling fractional crystallization produce bodies that are generally more mafic than the most mafic granites of the pluton and the residual melts have an almost haplogranitic composition, producing a bimodal compositional distribution not observed in the granites. Consequently, these two processes are ruled out. Filter-pressing fractional crystallization produces bodies in an onion-layer structure that become more felsic with increasing crystallization, culminating in a haplogranitic melt, and is able to reproduce the compositional trends of the granites, but only if the original magmas already had the composition of the granites. Filter-pressing fractionation produces a mineral assemblage that is 1.5 times more mafic than the magma fraction from which it is derived. However, the mineral assemblages produced by crystallization of an originally pure melt phase are still too felsic to account for the bulk of the granites of the Peninsula pluton. For filter-pressing to produce the most mafic granites of the pluton, the original magmas must already contain an entrained mafic mineral assemblage and have the same composition of the granites, otherwise the modelled trends do not match the maficity (FeO + MgO) or the slope against maficity of the granites. Crystallization of the magma in filter-pressing releases a free water phase, whose amount depends on the amount of water of the original magma, and whose behaviour may be controlled by a water-saturation front. In summary, the main control in the composition of S-type granites is the amount and nature of the entrained mineral assemblage, and filter-pressing fractional crystallization can only modify slightly the compositions of the granitic bodies derived from these magmas.

Lattice Boltzmann Simulation of Water Isotope Fractionation During Growth of Ice Crystals in Clouds

NASA Astrophysics Data System (ADS)

Lu, G.; Depaolo, D.; Kang, Q.; Zhang, D.

2006-12-01

The isotopic composition of precipitation, especially that of snow, plays a special role in the global hydrological cycle and in reconstruction of past climates using polar ice cores. The fractionation of the major water isotope species (HHO, HDO, HHO-18) during ice crystal formation is critical to understanding the global distribution of isotopes in precipitation. Ice crystal growth in clouds is traditionally treated with a spherically- symmetric steady state diffusion model, with semi-empirical modifications added to account for ventilation and for complex crystal morphology. Although it is known that crystal growth rate, which depends largely on the degree of vapor over-saturation, determines crystal morphology, there are no existing quantitative models that directly relate morphology to the vapor saturation factor. Since kinetic (vapor phase diffusion-controlled) isotopic fractionation also depends on growth rate, there should be a direct relationship between vapor saturation, crystal morphology, and crystal isotopic composition. We use a 2D Lattice-Boltzmann model to simulate diffusion-controlled ice crystal growth from vapor- oversaturated air. In the model, crystals grow solely according to the diffusive fluxes just above the crystal surfaces, and hence crystal morphology arises from the initial and boundary conditions in the model and does not need to be specified a priori. The input parameters needed are the isotope-dependent vapor deposition rate constant (k) and the water vapor diffusivity in air (D). The values of both k and D can be computed from kinetic theory, and there are also experimentally determined values of D. The deduced values of k are uncertain to the extent that the sticking coefficient (or accommodation coefficient) for ice is uncertain. The ratio D/k is a length that determines the minimum scale of dendritic growth features and allows us to scale the numerical calculations to atmospheric conditions using a dimensionless Damkohler number: Da = kh/D, where h is the width of the 2D calculation domain. Varying the nondimensional Da in the model is equivalent to varying the scale (h) in the model. Our calculations confirm that the crystal/vapor isotopic fractionation approaches the equilibrium value, and the crystals are compact (circular in 2D) as the saturation factor approaches unity (S= 1.0). At higher oversaturation (e.g. S = 1.2), dendritic crystals of millimeter size develop on timescales appropriate to cloud processes, the isotopic fractionations are dominated by kinetic effects, and similar to those predicted by the spherical diffusion model. Dendritic crystals are constrained to be relatively large, with dimension much greater than D/k. The most difficult aspect of the modeling is to account for the large density difference between air and ice, which requires us to use a fictitious higher density for the vapor-oversaturated air and scale the crystal growth time accordingly. A different approach, using a larger scale simulation to derive boundary conditions for a nested smaller scale calculation is in progress. The results to date clarify the controls on dendritic crystal growth, the relationships between saturation state, growth rate, crystal morphology and isotopic fractionation, and provide limits on the value of the accommodation coefficient.

Petrogenesis of calcic plagioclase megacrysts in Archean rocks

NASA Technical Reports Server (NTRS)

Phinney, W. C.; Morrison, D. A.

1986-01-01

Anorthositic complexes with large equidimensional plagioclase grains of highly calcic composition occur in nearly all Archean cratons. Similar plagioclase occur as megacrysts in many Archean sills, dikes, and volcanic flows. In the Canadian Shield these units occur throughout the Archean portions of the entire shield and are particularly common as dikes over an area of a few 100,000 sq km in Ontario and Manitoba during a period of at least 100 m.y. in many different rock types and metamorphic grades. The plagioclase generally occurs in three modes: as inclusions in mafic intrusions at various stages of fractionation, as crystal segregations in anorthosite complexes, or as megacrysts in fractionated sills, dikes, and flows. Most occurrences suggest that the plagioclase was formed elsewhere before being transported to its present location. The evidence seems to be quite clear that occurrences of these types of calcic plagioclase require: (1) ponding of a relatively undifferentiated Archean tholeiitic melt at some depth; (2) isothermal crystallization of large, equidimensional homogeneous plagioclase crystals; (3) separation of the plagioclase crystals from any other crystalline phases; (4) further fractionation of melt; (5)transport of various combinations of individual plagioclase crystals and clusters of crystals by variously fractionated melts; and (6) emplacement as various types of igneous intrusions or flows.

Experimental Fractional Crystallization of the Lunar Magma Ocean

NASA Technical Reports Server (NTRS)

Rapp, J. F.; Draper, D. S.

2012-01-01

The current paradigm for lunar evolution is of crystallization of a global scale magma ocean, giving rise to the anorthositic crust and mafic cumulate interior. It is thought that all other lunar rocks have arisen from this differentiated interior. However, until recently this paradigm has remained untested experimentally. Presented here are the first experimental results of fractional crystallization of a Lunar Magma Ocean (LMO) using the Taylor Whole Moon (TWM) bulk lunar composition [1].

Calculation of spontaneous emission from a V-type three-level atom in photonic crystals using fractional calculus

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

Huang, Chih-Hsien; Hsieh, Wen-Feng; Institute of Electro-Optical Science and Engineering, National Cheng Kung University, 1 Dahsueh Rd., Tainan 701, Taiwan

2011-07-15

Fractional time derivative, an abstract mathematical operator of fractional calculus, is used to describe the real optical system of a V-type three-level atom embedded in a photonic crystal. A fractional kinetic equation governing the dynamics of the spontaneous emission from this optical system is obtained as a fractional Langevin equation. Solving this fractional kinetic equation by fractional calculus leads to the analytical solutions expressed in terms of fractional exponential functions. The accuracy of the obtained solutions is verified through reducing the system into the special cases whose results are consistent with the experimental observation. With accurate physical results and avoidingmore » the complex integration for solving this optical system, we propose fractional calculus with fractional time derivative as a better mathematical method to study spontaneous emission dynamics from the optical system with non-Markovian dynamics.« less

Crystallization and dynamical arrest of attractive hard spheres.

PubMed

Babu, Sujin; Gimel, Jean-Christophe; Nicolai, Taco

2009-02-14

Crystallization of hard spheres interacting with a square well potential was investigated by numerical simulations using so-called Brownian cluster dynamics. The phase diagram was determined over a broad range of volume fractions. The crystallization rate was studied as a function of the interaction strength expressed in terms of the second virial coefficient. For volume fractions below about 0.3 the rate was found to increase abruptly with increasing attraction at the binodal of the metastable liquid-liquid phase separation. The rate increased until a maximum was reached after which it decreased with a power law dependence on the second virial coefficient. Above a critical percolation concentration, a transient system spanning network of connected particles was formed. Crystals were formed initially as part of the network, but eventually crystallization led to the breakup of the network. The lifetime of the transient gels increased very rapidly over a small range of interaction energies. Weak attraction destabilized the so-called repulsive crystals formed in pure hard sphere systems and shifted the coexistence line to higher volume fractions. Stronger attraction led to the formation of a denser, so-called attractive, crystalline phase. Nucleation of attractive crystals in the repulsive crystalline phase was observed close to the transition.

A fundamental dispute: A discussion of "On some fundamentals of igneous petrology" by Bruce D. Marsh, Contributions to Mineralogy and Petrology (2013) 166: 665-690

NASA Astrophysics Data System (ADS)

Latypov, Rais; Morse, Tony; Robins, Brian; Wilson, Richard; Cawthorn, Grant; Tegner, Christian; Holness, Marian; Lesher, Charles; Barnes, Steve; O'Driscoll, Brian; Veksler, Ilya; Higgins, Michael; Wilson, Allan; Namur, Olivier; Chistyakova, Sofya; Naslund, Richard; Thy, Peter

2015-02-01

Marsh (Contrib Miner Petrol 166:665-690, 2013) again claims that crystal-free basalt magmas are unable to differentiate in crustal magma chambers and regards layered intrusions as primarily due to the repeated emplacement of crystal suspensions. He ignores an earlier critique of his unconventional inferences (Latypov, J Petrol 50:1047-1069, 2009) as well as a wealth of petrographic, geochemical and experimental evidence supporting the dominant role of fractional crystallization in the solidification of layered intrusions. Most tellingly, the cryptic variations preserved in the Skaergaard and many other basaltic layered intrusions would require an exceedingly implausible sequence of phenocrystic magmas but are wholly consistent with in situ fractional crystallization. A major flaw in Marsh's hypothesis is that it dismisses progressive fractional crystallization within any magma chamber and hence prohibits the formation of crystal slurries with phenocrysts and melts that change systematically in composition in any feeder system. This inherent attribute of the hypothesis excludes the formation of layered intrusions anywhere.

Sb2Te3 and Its Superlattices: Optimization by Statistical Design.

PubMed

Behera, Jitendra K; Zhou, Xilin; Ranjan, Alok; Simpson, Robert E

2018-05-02

The objective of this work is to demonstrate the usefulness of fractional factorial design for optimizing the crystal quality of chalcogenide van der Waals (vdW) crystals. We statistically analyze the growth parameters of highly c axis oriented Sb 2 Te 3 crystals and Sb 2 Te 3 -GeTe phase change vdW heterostructured superlattices. The statistical significance of the growth parameters of temperature, pressure, power, buffer materials, and buffer layer thickness was found by fractional factorial design and response surface analysis. Temperature, pressure, power, and their second-order interactions are the major factors that significantly influence the quality of the crystals. Additionally, using tungsten rather than molybdenum as a buffer layer significantly enhances the crystal quality. Fractional factorial design minimizes the number of experiments that are necessary to find the optimal growth conditions, resulting in an order of magnitude improvement in the crystal quality. We highlight that statistical design of experiment methods, which is more commonly used in product design, should be considered more broadly by those designing and optimizing materials.

The Lunar Magma Ocean: Sharpening the Focus on Process and Composition

NASA Technical Reports Server (NTRS)

Rapp, J. F.; Draper, D. S.

2014-01-01

The currently accepted model for the formation of the lunar anorthositic crust is by flotation from a crystallizing lunar magma ocean (LMO) shortly following lunar accretion. Anorthositic crust is globally distributed and old, whereas the mare basalts are younger and derived from a source region that has experienced plagioclase extraction. Several attempts at modelling such a crystallization sequence have been made [e.g. 1, 2], but our ever-increasing knowledge of the lunar samples and surface have raised as many questions as these models have answered. This abstract presents results from our ongoing ex-periments simulating LMO crystallization and address-ing a range of variables. We investigate two bulk com-positions, which span most of the range of suggested lunar bulk compositions, from the refractory element enriched Taylor Whole Moon (TWM) [3] to the more Earth-like Lunar Primitive Upper Mantle (LPUM) [4]. We also investigate two potential crystallization mod-els: Fully fractional, where crystallizing phases are separated from the magma as they form and sink (or float in the case of plagioclase) throughout magma ocean solidification; and a two-step process suggested by [1, 5] with an initial stage of equilibrium crystalliza-tion, where crystals remain entrained in the magma before the crystal burden increases viscosity enough that convection slows and the crystals settle, followed by fractional crystallization. Here we consider the frac-tional crystallization part of this process; the equilibri-um cumulates having been determined by [6].

A survey of lunar rock types and comparison of the crusts of earth and moon

NASA Technical Reports Server (NTRS)

Wood, J. A.

1977-01-01

The principal known types of lunar rocks are briefly reviewed, and their chemical relationships discussed. In the suite of low-KREEP highland rocks, Fe/(Fe + Mg) in the normative mafic minerals increases and the albite content of normative plagio-clase decreases as the total amount of normative plagioclase increases, the opposite of the trend predicted by the Bowen reaction principle. The distribution of compositions of rocks from terrestrial layered mafic intrusives is substantially different: here the analyses fall in several discrete clusters (anorthositic rocks, norites, granophyres and ferrogabbros, ultramafics), and the chemical trends noted above are not reproduced. It is suggested that the observed trends in lunar highland rocks could be produced by crystal fractionation in a deep global surface magma system if (1) plagiociase tended to float, upon crystallization, and (2) the magma was kept agitated and well mixed (probably by thermal convection) until crystallization was far advanced and relatively little residual liquid was left. After the crustal system solidified, but before extensive cooling had developed a thick, strong lithosphere, mantle convection was able to draw portions of the lunar anorthositic crust down into the mantle.

Effect of hydrogen on deformation structure and properties of CMSX-2 nickel-base single-crystal superalloy

NASA Technical Reports Server (NTRS)

Dollar, M.; Bernstein, I. M.; Walston, S.; Prinz, F.; Domnanovich, A.

1987-01-01

Material used in this study was a heat of the alloy CMSX-2. This nickel-based superalloy was provided in the form of oriented single crystals, solutionized for 3 hrs at 1315 C. It was then usually heat treated as follows: 1050 C/16h/air cool + 850 C/48h/air cool. The resulting microstructure is dominated by cuboidal, ordered gamma precipitates with a volume fraction of about 75% and an average size of 0.5 microns. In brief, the most compelling hydrogen induced-changes in deformation structure are: (1) enhanced dislocation accumulation in the gamma matrix; and (2) more extensive cross-slip of superdislocations in the gamma precipitates. The enhanced dislocation density in gamma acts to decrease the mean free path of a superdislocation, while easier cross slip hinders superdislocation movement by providing pinning points in the form of sessile jobs. Both processes contribute to the increase of flow stress and the notable work hardening that occurs prior to fracture.

Space-Time Crystals of Trapped Ions

DTIC Science & Technology

2012-10-15

Spontaneous symmetry breaking can lead to the formation of time crystals, as well as spatial crystals. Here we propose a space- time crystal of...fields with fractional fluxes. The persistent rotation of trapped ions produces the temporal order, leading to the formation of a space- time crystal . We

Variation in trace element content of magnetite crystallized from a fractionating sulfide liquid, Sudbury, Canada: Implications for provenance discrimination

NASA Astrophysics Data System (ADS)

Dare, Sarah A. S.; Barnes, Sarah-Jane; Beaudoin, Georges

2012-07-01

Laser ablation ICP-MS analysis has been applied to many accessory minerals in order to understand better the process by which the rock formed and for provenance discrimination. We have determined trace element concentrations of Fe-oxides in massive sulfides that form Ni-Cu-PGE deposits at the base of the Sudbury Igneous Complex in Canada. The samples represent the crystallization products of fractionating sulfide liquids and consist of early-forming Fe-rich monosulfide solution (MSS) cumulates and residual Cu-rich intermediate solid solution (ISS). This study shows that Fe-oxide geochemistry is a sensitive petrogenetic indicator for the degree of fractionation of the sulfide liquid and provides an insight into the partitioning of elements between sulfide and Fe-oxide phases. In addition, it is useful in determining the provenance of detrital Fe-oxide. In a sulfide melt, all lithophile elements (Cr, Ti, V, Al, Mn, Sc, Nb, Ga, Ge, Ta, Hf, W and Zr) are compatible into Fe-oxide. The concentrations of these elements are highest in the early-forming Fe-oxide (titanomagnetite) which crystallized with Fe-rich MSS. Upon the continual crystallization of Fe-oxide from the sulfide liquid, the lithophile elements gradually decrease so that late-forming Fe-oxide (magnetite), which crystallized from the residual Cu-rich liquid, is depleted in these elements. This behavior is in contrast with Fe-oxides that crystallized from a fractionating silicate melt, whereby the concentration of incompatible elements, such as Ti, increases rather than decreases. The behavior of the chalcophile elements in magnetite is largely controlled by the crystallization of the sulfide minerals with only Ni, Co, Zn, Mo, Sn and Pb present above detection limit in magnetite. Nickel, Mo and Co are compatible in Fe-rich MSS and thus the co-crystallizing Fe-oxide is depleted in these elements. In contrast, magnetite that crystallized later from the fractionated liquid with Cu-rich ISS is enriched in Ni, Mo and Co because Fe-rich MSS is absent. The concentrations of Sn and Pb, which are incompatible with Fe-rich MSS, are highest in magnetite that formed from the fractionated Cu-rich liquid. At subsolidus temperatures, ilmenite exsolved from titanomagnetite whereas Al-spinel exsolved from the cores of some magnetite, locally redistributing the trace elements. However, during laser ablation ICP-MS analysis of these Fe-oxides both the magnetite and its exsolution products are ablated so that the analysis represents the original magmatic composition of the Fe-oxide that crystallized from the sulfide melt.

Plagioclase zonation styles in hornblende gabbro inclusions from Little Glass Mountain, Medicine Lake volcano, California: Implications for fractionation mechanisms and the formation of composition gaps

USGS Publications Warehouse

Brophy, J.G.; Dorais, M.J.; Donnelly-Nolan, J.; Singer, B.S.

1997-01-01

The rhyolite of Little Glass Mountain (73-74% SiO2) is a single eruptive unit that contains inclusions of quenched andesite liquid (54-61% SiO2) and partially crystalline cumulate hornblende gabbro (53-55% SiO2). Based on previous studies, the quenched andesite inclusions and host rhyolite lava are related to one another through fractional crystallization and represent an example of a fractionation-generated composition gap. The hornblende gabbros represent the cumulate residue associated with the rhyolite-producing and composition gap-forming fractionation event. This study combines textural (Nomarski Differential Interference Contrast, NDIC, imaging), major element (An content) and trace element (Mg, Fe, Sr, K, Ti, Ba) data on the style of zonation of plagioclase crystals from representative andesite and gabbro inclusions, to assess the physical environment in which the fractionation event and composition gap formation took place. The andesite inclusions (54-61% SiO2) are sparsely phyric with phenocrysts of plagioclase, augite and Fe-oxide??olivine, +/-orthopyroxene, +/-hornblende set within a glassy to crystalline matrix. The gabbro cumulates (53-55% SiO2) consist of an interconnected framework of plagioclase, augite, olivine, orthopyroxene, hornblende and Fe-oxide along with highly vesicular interstitial glass (70-74% SiO2). The gabbros record a two-stage crystallization history of plagioclase + olivine + augite (Stage I) followed by plagioclase+orthopyroxene + hornblende + Fe-oxide (Stage II). Texturally, the plagioclase crystals in the andesite inclusions are characterized by complex, fine-scale oscillatory zonation and abundant dissolution surfaces. Compositionally (An content) the crystals are essentially unzoned from core-to-rim. These features indicate growth within a dynamic (convecting?), reservoir of andesite magma. In contrast, the plagioclase crystals in the gabbros are texturally smooth and featureless with strong normal zonation from An74 at the core to around An30, K, and Ba abundances increase and Mg abundances decrease steadily towards the rim. Ti, Fe, and Sr abundances increase and then decrease towards the rim. The trace element variations are fully consistent with the two-stage crystallization sequence inferred from the gabbro mineralogy. These results indicate progressive closed-system in situ crystallization in a quiescent magmatic boundary layer environment located along the margins of the andesite magma body. The fractional crystallization that generated the host rhyolite lava is one of inward solidification of a crystallizing boundary layer followed by melt extraction and accumulation of highly evolved interstitial liquid. This mechanism explains the formation of the composition gap between parental andesite and rhyolite magma compositions.

LABORATORY AND FIELD EVALUATION OF CRYSTALLIZED DOW 704 OIL ON THE PERFORMANCE OF THE PM2.5 WINS FRACTIONATOR

EPA Science Inventory

Subsequent to the PM2.5 FRM's 1997 promulgation, technicians at the CT Dept. of Env. Protection observed that the DOW 704 diffusion oil used in the method's WINS fractionator would occasionally crystallize during field use - particularly under wintertime conditions. While the f...

New insights into the origin of the bimodal volcanism in the middle Okinawa Trough: not a basalt-rhyolite differentiation process

NASA Astrophysics Data System (ADS)

Zhang, Yuxiang; Zeng, Zhigang; Chen, Shuai; Wang, Xiaoyuan; Yin, Xuebo

2018-06-01

In the middle Okinawa Trough (MOT), rhyolites have been typically considered as products of crystallization differentiation of basaltic magma as a feature of bimodal volcanism. However, the evidence is insufficient. This paper compared chemical trends of volcanic rocks from the MOT with fractional crystallization simulation models and experimental results and utilized trace element modeling combined with Rayleigh fractionation calculations to re-examine fractional crystallization processes in generating rhyolites. Both qualitative and quantitative studies indicate that andesites, rather than rhyolites, originate by fractional crystallization from basalts in the MOT. Furthermore, we established two batch-melting models for the MOT rhyolites and proposed that type 1 rhyolites are produced by remelting of andesites with amphiboles in the residue, while type 2 rhyolites are derived from remelting of andesites without residual amphiboles. It is difficult to produce melts with a SiO2 content ranging from 62% to 68% either by magmatic differentiation from basalts or by remelting of andesites, and this difficulty might help account for the compositional gap (Daly gap) for bimodal volcanism in the Okinawa Trough.

Assessment of changes in crystallization properties of pressurized milk fat.

PubMed

Staniewski, Bogusław; Smoczyński, Michał; Staniewska, Katarzyna; Baranowska, Maria; Kiełczewska, Katarzyna; Zulewska, Justyna

2015-04-01

The aim of the study was to demonstrate the use of fractal image analysis as a possible tool to monitor the effect of pressurization on the crystallization pattern of anhydrous milk fat. This approach can be useful when developing new products based on milk fat. The samples were subjected to different hydrostatic pressure (100, 200, 300, and 400 MPa) and temperature (10 and 40 °C) treatments. The crystallization microphotographs were taken with a scanning electron microscope. The image analysis of scanning electron microscope photographs was done to determine a fractal dimension. Milk-fat pressurization under the applied parameters resulted in slight, but statistically significant, changes in the course of crystallization curves, related to the triacylglycerol fraction crystallizing in the lowest temperature (I exothermic effect). These changes were dependent on the value of pressure but not dependent on the temperatures applied during the process of pressurization (at either 10 or 40 °C). In turn, significant differences were observed in crystallization images of milk-fat samples subjected to this process compared with the control sample. The results of additional fractal analysis additionally demonstrated the highest degree of irregularity of the surface of the crystalline form for the nonpressurized sample and the samples pressurized at 200 and 300 MPa at 10 °C. The lowest value of fractal dimension-indicative of the least irregularity-was achieved for the fat samples pressurized at 400 MPa, 10 °C and at 100 MPa, 40 °C. The possibilities of wider application of the fractal analysis for the evaluation of effects of parameters of various technological processes on crystallization properties of milk fat require further extensive investigations. Copyright © 2015 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Iron Isotope Systematics of the Bushveld Complex, South Africa: Initial Results

NASA Astrophysics Data System (ADS)

Stausberg, N.; Lesher, C. E.; Hoffmann-Barfod, G.; Glessner, J. J.; Tegner, C.

2014-12-01

Iron isotopes show systematic changes in igneous rocks that have been ascribed to fractional crystallization, partial melting, as well as, diffusion effects. Layered mafic intrusions, such as the Paleoproterozoic Bushveld Igneous Complex, are ideally suited to investigate stable isotope fractionation arising principally by fractional crystallization. The upper 2.1km of the Bushveld Complex (Upper and Upper Main Zone, UUMZ) crystallized from a basaltic magma produced by a major recharge event, building up a sequence of tholeiitic, Fe-rich, gabbroic cumulate rocks that display systematic variations in mineralogy and mineral compositions consistent with fractional crystallization. Within this sequence, magnetite joins the liquidus assemblage at ˜260m, followed by olivine at 460m and apatite at 1000m. Here, we present iron isotope measurements of bulk cumulate rocks from the Bierkraal drill core of UUMZ of the western limb. Iron was chemically separated from its matrix and analyzed for δ56Fe (relative to IRMM- 014) with a Nu plasma MC-ICPMS at the University of California, Davis, using (pseudo-) high resolution and sample-standard bracketing. The δ56Fe values for Bushveld cumulates span a range from 0.04‰ to 0.36‰, and systematically correlate with the relative abundance of pyroxene + olivine, magnetite and plagioclase. Notably, the highest δ56Fe values are found in plagioclase-rich cumulates that formed prior to magnetite crystallization. δ56Fe is also high in magnetite-rich cumulates at the onset of magnetite crystallization, while subsequent cumulates exhibit lower and variable δ56Fe principally reflecting fractionation of and modal variations in magnetite, pyroxene and fayalitic olivine. The overall relationships for δ56Fe are consistent with positive mineral - liquid Fe isotope fractionation factors for magnetite and plagioclase, and negative to near zero values for pyroxene and olivine. These initial results are being integrated into a forward model of the Bushveld liquid line of descent and will be compared to complementary work on the Skaergaard intrusion.

Concanavalin A-binding cholesterol crystallization inhibiting and promoting activity in bile from patients with Crohn's disease compared to patients with ulcerative colitis.

PubMed

Keulemans, Y C; Mok, K S; Slors, J F; Brink, M A; Gouma, D J; Tytgat, G N; Groen, A K

1999-10-01

Crohn's disease is a risk factor for gallstone formation. In contrast, patients with ulcerative colitis have an incidence of gallstone formation comparable to the general population. The reason for this difference is not known. The aim of this study was to elucidate the factors controlling cholesterol crystallization in gallbladder bile of Crohn's disease and ulcerative colitis patients. Gallbladder bile was obtained by aspiration during bowel resections (26 Crohn's disease patients, 20 ulcerative colitis patients). Biliary lipid composition, crystal detection time and the effect of extraction of the concanavalin A-binding fraction on crystal formation were determined. Cholesterol crystals were present in seven of the 26 bile samples of Crohn's disease-patients and one of the 20 ulcerative colitis patients. Four of the bile samples of Crohn's disease patients were fast nucleating. None of the 20 ulcerative colitis patients had fast nucleating bile. Lipid composition, total lipid concentration and CSI were not significantly different between the two groups. In Crohn's disease patients extraction of concanavalin A-binding fraction decreased crystallization in 10 bile samples but accelerated crystallization in one bile sample. In eight bile samples from ulcerative colitis patients crystallization increased after concanavalin A-binding fraction extraction. Compared to ulcerative colitis patients, gallbladder bile of Crohn's disease patients showed increased cholesterol crystallization despite comparable lipid composition and cholesterol saturation index. This difference is caused by increased cholesterol crystallization-promoting activity. Bile from ulcerative colitis patients contains a Con A-binding factor which inhibits cholesterol crystallization.

Reduced-temperature crystallization of thin amorphous Fe80B20 films studied via empirical modeling of extended x-ray absorption fine structure

NASA Astrophysics Data System (ADS)

Harris, V. G.; Oliver, S. A.; Ayers, J. D.; Das, B. N.; Koon, N. C.

1996-04-01

The evolution of the local atomic environment around Fe atoms in very thin (15 nm), amorphous, partially crystallized and fully crystallized films of Fe80B20 was studied using extended x-ray absorption fine structure (EXAFS) measurements. The relative atomic fraction of each crystalline phase present in the annealed samples was extracted from the Fe EXAFS data by a least-squares fitting procedure, using data collected from t-Fe3B, t-Fe2B, and α-Fe standards. The type and relative fraction of the crystallization products follows the trends previously measured in Fe80B20 melt-spun ribbons, except for the fact that crystallization temperatures are ≊200 K lower than those measured in bulk equivalents. This greatly reduced crystallization temperature may arise from the dominant role of surface nucleation sites in the crystallization of very thin amorphous films.

Improving Student Understanding of Magmatic Differentiation Using an M&M Magma Chamber

NASA Astrophysics Data System (ADS)

Wirth, K. R.

2003-12-01

Many students, especially those in introductory geology courses, have difficulty developing a deep understanding of the processes of magmatic differentiation. In particular, students often struggle to understand Bowen's reaction series and fractional crystallization. The process of fractional crystallization by gravity settling can be illustrated using a model magma chamber consisting of M&M's. In this model, each major cation (e.g., Si, Ti, Al, Fe, Mg, Ca, Na, K) is represented by a different color M&M; other kinds of differently colored or shaped pieces could also be used. Appropriate numbers of each color M&M are combined to approximate the cation proportions of a basaltic magma. Students then fractionate the magma by moving M&M's to the bottom of the magma chamber forming a series of cumulus layers; the M&M's are removed in the stoichiometric proportions of cations in the crystallizing minerals (e.g., olivine, pyroxene, feldspars, quartz, magnetite, ilmenite). Students observe the changing cation composition (proportions of colors of M&M's) in the cumulus layers and in the magma chamber and graph the results using spreadsheet software. More advanced students (e.g., petrology course) can classify the cumulates and resulting liquid after each crystallization step, and they can compare the model system with natural magmatic systems (e.g., absence of important fractionating phases, volatiles). Students who have completed this exercise generally indicate a positive experience and demonstrate increased understanding of Bowen's reaction series and fractionation processes. They also exhibit greater familiarity with mineral stoichiometry, classification, solid-solution in minerals, element behavior (e.g., incompatibility), and chemical variation diagrams. Other models (e.g., paths of equilibrium and fractional crystallization on phase diagrams) can also be used to illustrate differentiation processes in upper level courses (e.g., mineralogy and petrology).

Fractional conductivity in 2D and 3D crystals

NASA Astrophysics Data System (ADS)

Sidharth, B. G.; Das, Abhishek; Valluri, S. R.

2018-04-01

In this work, we show that the phenomenon of fractional quantum Hall effect can be obtained for 2D and 3D crystal structures, using the noncommutative nature of spacetime and the Lambert W function. This fractional conductivity has been shown to be a consequence of the noncommutative geometry underlying the structure of graphene. Also, it has been shown, for graphene, that in the 3D case the conductivity is extremely small and depends on the self-energy that arises due to random fluctuations or zitterbewegung.

Phase equilibria constraints on the chemical and physical evolution of the campanian ignimbrite

USGS Publications Warehouse

Fowler, S.J.; Spera, F.J.; Bohrson, W.A.; Belkin, H.E.; de Vivo, B.

2007-01-01

The Campanian Ignimbrite is a > 200 km3 trachyte-phonolite pyroclastic deposit that erupted at 39.3 ?? 0.1 ka within the Campi Flegrei west of Naples, Italy. Here we test the hypothesis that Campanian Ignimbrite magma was derived by isobaric crystal fractionation of a parental basaltic trachyandesitic melt that reacted and came into local equilibrium with small amounts (5-10 wt%) of crustal rock (skarns and foid-syenites) during crystallization. Comparison of observed crystal and magma compositions with results of phase equilibria assimilation-fractionation simulations (MELTS) is generally very good. Oxygen fugacity was approximately buffered along QFM+1 (where QFM is the quartz-fayalite-magnetite buffer) during isobaric fractionation at 0.15 GPa (???6 km depth). The parental melt, reconstructed from melt inclusion and host clinopyroxene compositions, is found to be basaltic trachyandesite liquid (51.1 wt% SiO2, 9.3 wt% MgO, 3 wt% H2O). A significant feature of phase equilibria simulations is the existence of a pseudo-invariant temperature, ???883??C, at which the fraction of melt remaining in the system decreases abruptly from ???0.5 to < 0.1. Crystallization at the pseudo-invariant point leads to abrupt changes in the composition, properties (density, dissolved water content), and physical state (viscosity, volume fraction fluid) of melt and magma. A dramatic decrease in melt viscosity (from 1700 Pa s to ???200 Pa s), coupled with a change in the volume fraction of water in magma (from ??? 0.1 to 0.8) and a dramatic decrease in melt and magma density acted as a destabilizing eruption trigger. Thermal models suggest a timescale of ??? 200 kyr from the beginning of fractionation until eruption, leading to an apparent rate of evolved magma generation of about 10-3 km3/year. In situ crystallization and crystal settling in density-stratified regions, as well as in convectively mixed, less evolved subjacent magma, operate rapidly enough to match this apparent volumetric rate of evolved magma production. ?? Copyright 2007 Oxford University Press.

Phase equilibria modeling in igneous petrology: use of COMAGMAT model for simulating fractionation of ferro-basaltic magmas and the genesis of high-alumina basalt

NASA Astrophysics Data System (ADS)

Ariskin, Alexei A.

1999-05-01

A new version of COMAGMAT-3.5 model designed for computer simulations of equilibrium and fractional crystallization of basaltic magmas at low to high pressures is presented. The most important modifications of COMAGMAT include an ability to calculate more accurately the crystallization of magnetite and ilmenite, allowing the user to study numerically the effect of oxygen fugacity on basalt magma fractionation trends. Methodological principles of the use of COMAGMAT were discussed based on its thermodynamical and empirical basis, including specific details of the model calibration. Using COMAGMAT-3.5 a set of phase equilibria calculations (called Geochemical Thermometry) has been conducted for six cumulative rocks from the Marginal Border Series of the Skaergaard intrusion. As a result, initial magma temperature (1165±10°C) and trapped melt composition proposed to be parental magma to the Skaergaard intrusion were determined. Computer simulations of perfect fractionation of this composition as well as another proposed parent produced petrochemical trends opposite to those followed from natural observations. This is interpreted as evidence for an initial Skaergaard magma containing a large amount of olivine and plagioclase crystals (about 40-45%), so that the proposed and calculated parents are related through the melt trapped in the crystal-liquid mixture. This promotes the conclusion that the Skaergaard magma fractionation process was intermediate between equilibrium and fractional crystallization. In this case the classic Wager's trend should be considered an exception rather than a rule for the differentiation of ferro-basaltic magmas. A polybaric version of COMAGMAT has been applied for the genetic interpretation of a volcanic suite from the Klyuchevskoi volcano, Kamchatka, Russia. To identify petrological processes responsible for the observed suite ranging from high-magnesia to high-alumina basalts, we used the model to simulate the Klyuchevskoi suite assuming isobaric crystallization of a parental HMB magma at a variety of pressures and a separate set of simulations assuming fractionation during continuous magma ascent from a depth of 60 km. These results indicate that the Klyuchevskoi trend can be produced by ˜40% fractionation of Ol-Aug-Sp±Opx assemblages during ascent of the parental HMB magma over the pressure range 19-7 kbar with the rate of decompression being 0.33 kbar/% crystallized (at 1350-1110°C), with ˜2 wt.% of H 2O in the initial melt and ˜3 wt.% of H 2O in the resultant high-Al basalt.

Crystal fractionation in the SNC meteorites: Implications for sample selection

NASA Technical Reports Server (NTRS)

Treiman, Allan H.

1988-01-01

Almost all rock types in the SNC meteorites are cumulates, products of magma differentiation by crystal fractionation (addition or removal of crystals). If the SNC meteorites are from the surface of Mars or near subsurface, then most of the igneous units on Mars are differentiated. Basaltic units probably experienced minor to moderate differientation, but ultrabasic units probably experienced extreme differentiation. Products of this differentiation may include Fe-rich gabbro, pyroxenite, periodotite (and thus serpentine), and possibly massive sulfides. The SNC meteorites include ten lithologies (three in EETA79001), eight of which are crystal cumulates. The other lithologies, EETA79001 A and B are subophitic basalts.

Reconstructing fluid-flow events in Lower-Triassic sandstones of the eastern Paris Basin by elemental tracing and isotopic dating of nanometric illite crystals

NASA Astrophysics Data System (ADS)

Blaise, Thomas; Clauer, Norbert; Cathelineau, Michel; Boiron, Marie-Christine; Techer, Isabelle; Boulvais, Philippe

2016-03-01

Lower- to Middle-Triassic sandstones from eastern Paris Basin were buried to a maximum depth of 2500 m at a paleo-temperature of about 100 °C. They contain extensive amounts of authigenic platy and filamentous illite particles similar to those reported in reservoirs generally buried at 3000 to -5000 m and subjected to temperatures of 120 to -150 °C. To evaluate this unexpected occurrence, such sandstones were collected from drill cores between 1825 and 2000 m depth, and nanometric-sized sub-fractions were separated. The illite crystals were identified by XRD, observed by SEM and TEM, analyzed for their major, trace, rare-earth elements and oxygen isotope compositions, and dated by K-Ar and Rb-Sr. Illite particles display varied growth features in the rock pore-space and on authigenic quartz and adularia that they postdate. TEM-EDS crystal-chemical in situ data show that the illite lath/fiber and platelet morphologies correspond at least to two populations with varied interlayer charges: between 0.7 and 0.9 for the former and between 0.8 and 1.0 for the latter, the Fe/Fe + Mg ratio being higher in the platelets. Except for the deeper conglomerate, the PAAS-normalized REE patterns of the illite crystals are bell-shaped, enriched in middle REEs. Ca-carbonates and Ca-phosphates were detected together with illite in the separates. These soluble components yield 87Sr/86Sr ratios that are not strictly in chemical equilibrium with the illite crystals, suggesting successive fluids flows with different chemical compositions. The K-Ar data of finer <0.05 μm illite separates confirm two crystallization events at 179.4 ± 4.5 and 149.4 ± 2.5 Ma during the Early and Late Jurassic. The slightly coarser fractions contain also earlier crystallized or detrital K-bearing minerals characterized by lower δ18O values. The δ18O of the finest authigenic illite separates tends to decrease slightly with depth, from 18.2 (±0.2) to 16.3 (±0.2)‰, suggesting different but contemporaneous crystallization conditions deeper in the section. The illite platelets and filaments crystallized in changing physical-chemical crystallization conditions induced by fluids flows through the host-rock pore system. These flow events were probably driven by repetitive rifting episodes of the North Atlantic Ocean, although located several hundreds kilometers away from eastern Paris Basin, and/or by fracturing events in the nearby basement of the Vosges Massif. Complex relationships between geodynamical events, thermal anomalies, and advective fluids confirm that remote tectonic activities can impact quiescent basins, even if located far from tectono-thermal activities, by discrete and long-distance fluid flows.

The Origin of Tholeiitic and Calc-Alkaline Trends in Arc Magmas

NASA Astrophysics Data System (ADS)

Luffi, P. I.; Lee, C.

2012-12-01

It has long been recognized that tholeiitic (TH, high-Fe/Mg) and calc-alkaline (CA, low-Fe/Mg) magmatic series define the two most important igneous differentiation trends shaping Earth's crust. While oceanic crust formation at mid-ocean ridges is typically confined to a TH trend, arc magmatism at convergent margins, considered to significantly contribute to continent formation, generates both TH and CA trends. Thus, the origin of these trends - a key issue to understanding how continental crust forms - is matter of ongoing debate. Prevalent factors thought to contribute to the TH-CA duality are: 1) redox conditions (oxygen fugacity, fO2) and H2O contents in magmas, which control the onset and abundance of high-Fe/Mg oxide mineral fractionation; 2) crystallization depths that regulate the fractionating solid assemblage and thereby the solid/liquid Kd(Fe-Mg). Relying on an extensive geochemical dataset of modern arc volcanics and thermodynamic phase equilibria modeling, here we examine the validity and relative importance of these factors in arc petrogenesis. First, to discriminate igneous rocks more efficiently, we formulate an improved CA/TH index solely based on FeO-MgO systematics. We then confirm on a quantitative basis that, on regional scales, arcs formed on thick crust tend to be more calk-alkaline than those emplaced on thinner crust are, and show that the effect of fO2 on the CA/TH index in arc magmas is more significant than that of H2O. Importantly, we demonstrate that CA trends typical for continental arcs only form when crystal fractionation is accompanied by the assimilation of oxidized crustal components; in the absence of buffering oxidized assimilants fractionating magmas follow a TH trend more common in island arcs, irrespective of their H2O content and initial fO2 level. We find that high-pressure fractionation of amphibole and garnet in arc magmas occurs too late to have a significant influence on the CA/TH index; in addition, garnet-melt and amphibole-melt Kd(Fe-Mg) values may be too low to account for CA trends observed in thick continental arcs. Hence, depths of crystallization do not appear to influence the CA/TH index directly. We speculate that typical island arcs are dominantly tholeiitic because here crustal assimilation is inhibited and magma throughput is enhanced by extensional tectonic regimes. In contrast, the dominantly calc-alkaline nature of thicker continental arcs may be the consequence of efficient assimilation of oxidized crustal materials in a compressional environment restraining magma throughput.

Thermal and petrologic constraints on the lower crustal melt accumulation in the Salton Sea Geothermal Field

NASA Astrophysics Data System (ADS)

Karakas, O.; Dufek, J.; Mangan, M.; Wright, H. M. N.

2014-12-01

Heat transfer in active volcanic areas is governed by complex coupling between tectonic and magmatic processes. These two processes provide unique imprints on the petrologic and thermal evolution of magma by controlling the geometry, depth, longevity, composition, and fraction of melt in the crust. The active volcanism, tectonic extension, and significantly high surface heat flow in Salton Sea Geothermal Field, CA, provides information about the dynamic heat transfer processes in its crust. The volcanism in the area is associated with tectonic extension over the last 500 ka, followed by subsidence and sedimentation at the surface level and dike emplacement in the lower crust. Although significant progress has been made describing the tectonic evolution and petrology of the erupted products of the Salton Buttes, their coupled control on the crustal heat transfer and feedback on the melt evolution remain unclear. To address these concepts, we develop a two-dimensional finite volume model and investigate the compositional and thermal evolution of the melt and crust in the Salton Sea Geothermal Field through a one-way coupled thermal model that accounts for tectonic extension, lower crustal magma emplacement, sedimentation, and subsidence. Through our simulations, we give quantitative estimates to the thermal and compositional evolution and longevity of the lower crustal melt source in the crustal section. We further compare the model results with petrologic constraints. Our thermal balance equations show that crustal melting is limited and the melt is dominated by mantle-derived material. Similarly, petrologic work on δ18O isotope ratios suggests fractional crystallization of basalt with minor crustal assimilation. In addition, we suggest scenarios for the melt fraction, composition, enthalpy release, geometry and depth of magma reservoirs, their temporal evolution, and the timescales of magmatic storage and evolution processes. These parameters provide the source conditions for the dynamics of surface volcanism and the presence of a geothermal system, which modify the thermal and mechanical structure of the crust.

Magma Differentiation and Storage Inferred from Crystal Textures at Harrat Rahat Volcanic Field, Kingdom of Saudi Arabia

NASA Astrophysics Data System (ADS)

Witter, M. R.; Mahood, G. A.; Stelten, M. E.; Downs, D. T.; Zahran, H. M.

2015-12-01

We present results of a petrographic study of Harrat Rahat volcanic field in western Saudi Arabia as part of a collaborative project between the U.S.G.S. and the Saudi Geological Survey. Lavas range in composition from alkali basalt to trachyphonolite. Basalts have <2-10 vol.% phenocrysts of euhedral olivine and plagioclase (± minor clinopyroxene). In intermediate lavas, phenocrysts (<5 vol.%) of olivine and plagioclase are resorbed, and plagioclase also exhibits sieve textures and strong zoning, indicative of complex magmatic histories. Trachyphonolite lavas have 0-35 vol.% large phenocrysts of anorthoclase and trace fayalitic olivine but are characterized by a size distribution of crystals that is seriate in hand specimen, so that most exceeded 45% crystals at the time of eruption. Some contain groundmass alkali amphibole. Crystal size distributions (CSD) of crystal-rich trachyphonolites produce simple linear trends (see below), which are interpreted as signifying that all the crystals are related through a common nucleation and growth history, at more or less constant pressure. Linear CSDs indicate no loss of small crystals due to reheating of magmas by recharge, no gain of small crystals due to late-stage nucleation on ascent or degassing, and no addition of large phenocrysts by crystal accumulation or magma mixing. Experimental studies demonstrate that silica-undersaturated evolved magmas like those erupted at Harrat Rahat can form by fractionation of alkali basalts at crustal depths greater than ~25 km. The observed phenocryst assemblage in the trachyphonolites, however, forms at shallow depths, ~2-4 km, according to MELTS modeling. Coupled with CSD data, this suggests that deep extraction events yield crystal-poor trachyphonolite magmas that rise to the upper crust where they undergo crystallization. Extensive shallow crystallization of trachyphonolites may have triggered eruptions by causing vapor saturation, which lowers magma density via vesiculation and has the potential to explosively disrupt wallrocks. Based on the complex crystal textures in the intermediate lavas and their similarity in age to the trachyphonolites, ~120 ka, we suggest that most of the intermediate magmas form by magma mixing when rising basalts intercept and entrain shallow trachyphonolite magma.

SU-C-201-01: Investigation of the Effects of Scintillator Surface Treatment On Light Output Measurements with SiPM Detectors

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

Valenciaga, Y; Prout, D; Chatziioannou, A

2015-06-15

Purpose: To examine the effect of different scintillator surface treatments (BGO crystals) on the fraction of scintillation photons that exit the crystal and reach the photodetector (SiPM). Methods: Positron Emission Tomography is based on the detection of light that exits scintillator crystals, after annihilation photons deposit energy inside these crystals. A considerable fraction of the scintillation light gets trapped or absorbed after going through multiple internal reflections on the interfaces surrounding the crystals. BGO scintillator crystals generate considerably less scintillation light than crystals made of LSO and its variants. Therefore, it is crucial that the small amount of light producedmore » by BGO exits towards the light detector. The surface treatment of scintillator crystals is among the factors affecting the ability of scintillation light to reach the detectors. In this study, we analyze the effect of different crystal surface treatments on the fraction of scintillation light that is detected by the solid state photodetector (SiPM), once energy is deposited inside a BGO crystal. Simulations were performed by a Monte Carlo based software named GATE, and validated by measurements from individual BGO crystals coupled to Philips digital-SiPM sensor (DPC-3200). Results: The results showed an increment in light collection of about 4 percent when only the exit face of the BGO crystal, is unpolished; compared to when all the faces are polished. However, leaving several faces unpolished caused a reduction of at least 10 percent of light output when the interaction occurs as far from the exit face of the crystal as possible compared to when it occurs very close to the exit face. Conclusion: This work demonstrates the advantages on light collection from leaving unpolished the exit face of BGO crystals. The configuration with best light output will be used to obtain flood images from BGO crystal arrays coupled to SiPM sensors.« less

Diffusion-driven magnesium and iron isotope fractionation in Hawaiian olivine

USGS Publications Warehouse

Teng, F.-Z.; Dauphas, N.; Helz, R.T.; Gao, S.; Huang, S.

2011-01-01

Diffusion plays an important role in Earth sciences to estimate the timescales of geological processes such as erosion, sediment burial, and magma cooling. In igneous systems, these diffusive processes are recorded in the form of crystal zoning. However, meaningful interpretation of these signatures is often hampered by the fact that they cannot be unambiguously ascribed to a single process (e.g., magmatic fractionation, diffusion limited transport in the crystal or in the liquid). Here we show that Mg and Fe isotope fractionations in olivine crystals can be used to trace diffusive processes in magmatic systems. Over sixty olivine fragments from Hawaiian basalts show isotopically fractionated Mg and Fe relative to basalts worldwide, with up to 0.4??? variation in 26Mg/24Mg ratios and 1.6??? variation in 56Fe/54Fe ratios. The linearly and negatively correlated Mg and Fe isotopic compositions [i.e., ??56Fe=(??3.3??0.3)????26Mg], co-variations of Mg and Fe isotopic compositions with Fe/Mg ratios of olivine fragments, and modeling results based on Mg and Fe elemental profiles demonstrate the coupled Mg and Fe isotope fractionation to be a manifestation of Mg-Fe inter-diffusion in zoned olivines during magmatic differentiation. This characteristic can be used to constrain the nature of mineral zoning in igneous and metamorphic rocks, and hence determine the residence times of crystals in magmas, the composition of primary melts, and the duration of metamorphic events. With improvements in methodology, in situ isotope mapping will become an essential tool of petrology to identify diffusion in crystals. ?? 2011 Elsevier B.V.

Geochemical studies of abyssal lavas recovered by DSRV Alvin from Eastern Galapagos Rift, Inca Transform, and Ecuador Rift: 2. Phase chemistry and crystallization history

NASA Astrophysics Data System (ADS)

Perfit, Michael R.; Fornari, Daniel J.

1983-12-01

A diverse suite of lavas recovered by DSRV Alvin from the eastern Galapagos rift and Inca transform includes mid-ocean ridge tholeiitic basalts (MORB), iron- and titanium-enriched basalts (FeTi basalts), and abyssal andesites. Rock types transitional in character (ferrobasalts and basaltic andesites) were also recovered. The most mafic glassy basalts contain plagioclase, augite, and olivine as near-liquidus phases, whereas in more fractionated basalts, pigeonite replaces olivine and iron-titanium oxides crystallize. Plagioclase crystallizes after pyroxenes and iron-titanium oxides in andesites, possibly due to increased water contents or cooling rates. Apatite phenocrysts are present in some andesitic glasses. Ovoid sulfide globules are also common in many lavas. Compositional variations of phenocrysts in glassy lavas reflect changes in magma chemistry, temperature of crystallization, and cooling rate. The overall chemical variations parallel the chemical evolution of the lava suite and are similar to those in other fractionated tholeiitic complexes. Elemental partitioning between plagioclase-, pyroxene-, and olivine-glass pairs suggests that equilibration occurred at low pressure in a rather restricted temperature range. Various geothermometers indicate that the most primitive MORB began to crystallize between 1150° and 1200°C with fo2 < 10-7 atm. Coexisting iron-titanium oxides in more evolved lavas yield temperatures ˜1025°C to as low as 910°C withfo2 from 10-8 to 10-12 atm. PH 2 o could have been as high as 1 kbar during andesite crystallization. Compositions of the lavas from the Galapagos rift follow the experimentally determined (1 atm-QFM) liquid line of descent. Least squares calculations for the major elements indicate that the entire suite of lavas can be produced by fractional crystallization of successive residual liquids from a MORB parent magma. FeTi basalts represent 30-65 cumulative weight percent crystallization of plagioclase, augite, and olivine. An additional 30-50% fractionation of pyroxenes, plagioclase, titanomagnetite, and possible apatite is required to generate andesite from FeTi basalt liquids. The presence of partially resorbed mafic xenocrysts in some andesites, FeTi basalt inclusions in these xenocrysts, high-silica glass inclusions in basaltic andesites, and the transitional chemistry of basaltic andesites are evidence that some magma mixing occurred during crystal fractionation. The diversity of lava types recovered at single dive sites suggests that low-pressure fractional crystallization is a very efficient process beneath the eastern Galapagos rift and that isolated magma bodies must be present at shallow levels beneath the accretionary locus. Voluminous FeTi basalts erupted at the rift-transform intersection are genetically related to the rift lavas, but their restricted chemistry reflects different thermal and tectonic controls on their petrogenesis.

Investigations on solid-solid phase transformation of 5-methyl-2-[(4-methyl-2-nitrophenyl)amino]-3-thiophenecarbonitrile.

PubMed

Li, Hui; Stowell, Joseph G; He, Xiaorong; Morris, Kenneth R; Byrn, Stephen R

2007-05-01

Solid-solid transformation of 5-methyl-2-[(4-methyl-2-nitrophenyl)amino]-3-thiophenecarbonitrile from the dark-red to the red form was investigated. By controlled crystallization, the dark-red form was prepared and the crystals were sieved into fractions: coarse (>250 microm), medium (125-177 microm), and fine (<88 microm). The transformation rate order (fastest to slowest) of the different fractions is coarse > medium > fine. However, milling accelerates the transformation, that is, smaller particles generated by milling transforms faster. Furthermore, ethanol vapor annealing slows both the transformation of the coarse and medium fractions, especially the latter. Therefore, the mechanism of transformation is not directly related to the crystal-size and most likely related to the amount and activity of the defects in the crystals. The three-dimensional (3-D) Avrami-Erofe'ev model, know as "random nucleation and growth" model, fits the kinetics of coarse fraction best. Higher relative humidity accelerates the transformation dramatically even though the compound is highly-hydrophobic. With minimal hydrogen bonding interaction involved, it appears even small amounts of water can serve as a nucleation catalyst by binding to the crystal surface, especially at defect sites, thus increasing the molecular mobility of these sites, promoting the transformation to the second phase and thereby increasing the transformation rate. (c) 2007 Wiley-Liss, Inc. and the American Pharmacists Association.

Dacite petrogenesis on mid-ocean ridges: Evidence for oceanic crustal melting and assimilation

USGS Publications Warehouse

Wanless, V.D.; Perfit, M.R.; Ridley, W.I.; Klein, E.

2010-01-01

Whereas the majority of eruptions at oceanic spreading centers produce lavas with relatively homogeneous mid-ocean ridge basalt (MORB) compositions, the formation of tholeiitic andesites and dacites at mid-ocean ridges (MORs) is a petrological enigma. Eruptions of MOR high-silica lavas are typically associated with ridge discontinuities and have produced regionally significant volumes of lava. Andesites and dacites have been observed and sampled at several locations along the global MOR system; these include propagating ridge tips at ridge-transform intersections on the Juan de Fuca Ridge and eastern Gal??pagos spreading center, and at the 9??N overlapping spreading center on the East Pacific Rise. Despite the formation of these lavas at various ridges, MOR dacites show remarkably similar major element trends and incompatible trace element enrichments, suggesting that similar processes are controlling their chemistry. Although most geochemical variability in MOR basalts is consistent with low-pressure fractional crystallization of various mantle-derived parental melts, our geochemical data for MOR dacitic glasses suggest that contamination from a seawater-altered component is important in their petrogenesis. MOR dacites are characterized by elevated U, Th, Zr, and Hf, low Nb and Ta concentrations relative to rare earth elements (REE), and Al2O3, K2O, and Cl concentrations that are higher than expected from low-pressure fractional crystallization alone. Petrological modeling of MOR dacites suggests that partial melting and assimilation are both integral to their petrogenesis. Extensive fractional crystallization of a MORB parent combined with partial melting and assimilation of amphibole-bearing altered crust produces a magma with a geochemical signature similar to a MOR dacite. This supports the hypothesis that crustal assimilation is an important process in the formation of highly evolved MOR lavas and may be significant in the generation of evolved MORB in general. Additionally, these processes are likely to be more common in regions of episodic magma supply and enhanced magma-crust interaction such as at the ends of ridge segments. ?? The Author 2010. Published by Oxford University Press. All rights reserved.

Aerosol-Cloud Interactions during Tropical Deep Convection: Evidence for the Importance of Free Tropospheric Aerosols

NASA Technical Reports Server (NTRS)

Ackerman, A.; Jensen, E.; Stevens, D.; Wang, D.; Heymsfield, A.; Miloshevich, L.; Twohy, C.; Poellot, M.; VanReken, T.; Fridland, Ann

2003-01-01

NASA's 2002 CRYSTAL-FACE field experiment focused on the formation and evolution of tropical cirrus cloud systems in southern Florida. Multiple aircraft extensively sampled cumulonimbus dynamical and microphysical properties, as well as characterizing ambient aerosol populations both inside and outside the full depth of the convective column. On July 18, unique measurements were taken when a powerful updraft was traversed directly by aircraft, providing a window into the primary source region of cumulonimbus anvil crystals. Observations of the updraft, entered at approximately l0 km altitude and -34 C, indicated more than 200 cloud particles per mL at vertical velocities exceeding 20 m/s and the presence of significant condensation nuclei and liquid water within the core. In this work, aerosol and cloud phase observations are integrated by simulating the updraft conditions using a large-eddy resolving model with 3 explicit multiphase microphysics, including treatment of size-resolved aerosol fields, aerosol activation and freezing, and evaporation of cloud particles back to the aerosol phase. Simulations were initialized with observed thermodynamic and aerosol size distributions profiles and convection was driven by surface fluxes assimilated from the ARPS forecast model. Model results are consistent with the conclusions that most crystals are homogeneously frozen droplets and that entrained free tropospheric aerosols may contribute a significant fraction of the crystals. Thus most anvil crystals appear to be formed aloft in updraft cores, well above cloud base. These conclusions are supported by observations of hydrometeor size distribution made while traversing the dore, as well as aerosol and cloud particle size distributions generally observed by aircraft below 4km and crystal properties generally observed by aircraft above 12km.

Trondhjemitic melts produced by in-situ differentiation of a tholeiitic lava flow, Reykjanes Peninsula, Iceland.

NASA Astrophysics Data System (ADS)

Martin, E.; Sigmarsson, O.

2006-12-01

How the continental crust began to form early in Earth's history is unconstrained. However, it is reasonable to presume that higher heat flow in the past, resulted in more frequent interaction of mantle plumes and mid- oceanic ridges. If true, then Iceland could be a good analogue for processes occurring on Earth at its youth stage. This is supported by the relatively high abundance of silicic rocks in Iceland but their rarity on other oceanic hot spots. The origin of Icelandic silicic rocks has been a subject of a lively debate but has been shown to be principally formed by partial melting of hydrothermally altered basaltic crust. However, in rare cases, their origin by fractional crystallization from mantle derived basalts is suggested. Segregation veins in lava flows frequently contain interstitial glasses of silicic compositions. Moreover, they allow an exceptional overview of the fractional crystallization mechanism. These veins form by gas filter pressing during cooling and degassing of solidifying lava flows, after approximately 50% fractional crystallization of anhydrous minerals. Pairs of samples, host lava and associated segregation veins, from Reykjanes Peninsula (Iceland), Lanzarote (Canary Island) and Masaya's volcano (Nicaragua), allow the assessment of a near-complete fractional crystallization of olivine tholeiitic basalt at pressure close to one atmosphere. Interstitial glass patches in segregation veins represent the final product of this process (80 97 % of fractional crystallization). These ultimate liquids are of granitic composition in the case of Lanzarote and Masaya but overwhelmingly trondhjemitic at Reykjanes. It appears that the initial K2O/Na2O of the basaltic liquid controls the evolution path of the residual liquid composition produced at pressure close to 0.1 MPa (1 bar). Granitic liquids are generated from basalts of high initial K2O/Na2O whereas low initial K2O/Na2O leads to trondhjemitic compositions. The trondhjemitic composition of glass patches from the segregation vein at Reykjanes Peninsula differs from Icelandic silicic magmas but is close to those of the Archaean TTG (trondhjemite-tonalite-granodiorite) suite. Taken at face value, this may imply that fractional crystallisation of olivine tholeiites (low K2O/Na2O) could have played a significant role during the formation of the early continental crust. At higher pressure, where garnet is on liquidus, fractional crystallisation can generate the observed trace element patterns observed in TTG. The progressive cooling, crystallization and degassing of basaltic magma ocean, thought to have been prevailing during the Hadean, could have led to high degree of fractional crystallization producing significant volume of trondhjemitic melts that because of its buoyancy contributed to the formation of the earliest continental crust.

Numerical simulation of flow and melting characteristics of seawater-ice crystals two-phase flow in inlet straight pipe of shell and tube heat exchanger of polar ship

NASA Astrophysics Data System (ADS)

Xu, Li; Huang, Chang-Xu; Huang, Zhen-Fei; Sun, Qiang; Li, Jie

2018-05-01

The ice crystal particles are easy to enter into the seawater cooling system of polar ship together with seawater when it sails in the Arctic. They are easy to accumulate in the pipeline, causing serious blockage of the cooling pipe. In this study, the flow and melting characteristics of ice particles-seawater two-phase flow in inlet straight pipe of shell-and-tube heat exchanger were numerically simulated by using Eulerian-Eulerian two-fluid model coupled with the interphase heat and mass transfer model. The influences of inlet ice packing factor, ice crystal particle diameter, and inlet velocity on the distribution and melting characteristics of ice crystals were investigated. The degree of asymmetry of the distribution of ice crystals in the cross section decreases gradually when the IPF changes from 5 to 15%. The volume fractions of ice crystals near the top of the outlet cross section are 19.59, 19.51, and 22.24% respectively for ice packing factor of 5, 10 and 15%. When the particle diameter is 0.5 mm, the ice crystals are gradually stratified during the flow process. With particle diameters of 1.0 and 2.0 mm, the region with the highest volume fraction of ice crystals is a small circle and the contours in the cloud map are compact. The greater the inlet flow velocity, the less stratified the ice crystals and the more obvious the turbulence on the outlet cross section. The average volume fraction of ice crystals along the flow direction is firstly rapidly reduced and then stabilized after 300 mm.

Optical properties of anisotropic 3D nanoparticles arrays

NASA Astrophysics Data System (ADS)

Santiago, E. Y.; Esquivel-Sirvent, R.

2017-07-01

The optical properties of 3D periodic arrays of spheroidal Au nanoparticles are calculated using a Bruggeman effective medium approximation. The optical response of the supra-crystal depends on the volume fraction of the nanoparticles and their aspect or size ratio (major/minor axis). All the nanoparticles have the same orientation, and this defines an anisotropic dielectric function of the crystal. As a function of the filling fraction, while keeping the size ratio fixed, the maximum in the extinction spectra along the major and minor axes does not show a significant change. However, for a fixed filling fraction, varying the aspect ratio of the particles induces a shift of several hundred of nanometers in the maximum of the extinction spectra along the major axis and almost no changes along the minor axis. Depending on the aspect ratio and the filling fraction, we show that the supra-crystal has three regimes with different values of an effective plasma frequency. Contribution to the Focus Issue Self-assemblies of Inorganic and Organic Nanomaterials edited by Marie-Paule Pileni.

Twenty years of molecular beam epitaxy

NASA Astrophysics Data System (ADS)

Cho, A. Y.

1995-05-01

The term "molecular beam epitaxy" (MBE) was first used in one of our crystal growth papers in 1970, after having conducted extensive surface physics studies in the late 1960's of the interaction of atomic and molecular beams with solid surfaces. The unique feature of MBE is the ability to prepare single crystal layers with atomic dimensional precision. MBE sets the standard for epitaxial growth and has made possible semiconductor structures that could not be fabricated with either naturally existing materials or by other crystal growth techniques. MBE led the crystal growth technologies when it prepared the first semiconductor quantum well and superlattice structures that gave unexpected and exciting electrical and optical properties. For example, the discovery of the fractional quantized Hall effect. It brought experimental quantum physics to the classroom, and practically all major universities throughout the world are now equipped with MBE systems. The fundamental principles demonstrated by the MBE growth of III-V compound semiconductors have also been applied to the growth of group IV, II-VI, metal, and insulating materials. For manufacturing, the most important criteria are uniformity, precise control of the device structure, and reproducibility. MBE has produced more lasers (3 to 5 million per month for compact disc application) than any other crystal growth technique in the world. New directions for MBE are to incorporate in-situ, real-time monitoring capabilities so that complex structures can be precisely "engineered". In the future, as environmental concerns increase, the use of toxic arsine and phosphine may be limited. Successful use of valved cracker cells for solid arsenic and phosphorus has already produced InP based injection lasers.

Magma Chamber of the 26.5 ka Oruanui Eruption, Taupo Volcano, New Zealand

NASA Astrophysics Data System (ADS)

Liu, Y.; Anderson, A. T.; Wilson, C. J.; Davis, A. M.

2004-12-01

We have investigated melt inclusions and their host quartz crystals from the Bishop-Tuff-sized 26.5 ka Oruanui eruption at Taupo volcano, New Zealand. Compositions (major and trace elements, H2O and CO2) of melt inclusions and cathodoluminescence (CL) images of quartz were obtained for eight individual pumices from early, middle and late depositional units. All melt inclusions are high-silica weakly peraluminous rhyolites. Melt inclusions for different eruptive phases have similar ranges of H2O contents (3.8-5.2 wt %), but late-erupted samples have higher CO2 contents (mostly > 140 ppm). A positive correlation between CO2 and compatible trace elements such as Sr suggests that crystallization and melt entrapment occurred under gas-saturated conditions. Trace elements variations in melt inclusions are consistent with fractionation of 30-40 wt % crystals (plagioclase+quartz+pyroxene+amphibole). Crystal contents in pumices, trace-element contents in melt inclusions, and CL zoning patterns of quartz show no correlation with eruptive phases, suggesting that the Oruanui magma was well mixed before eruption. Some Oruanui quartz crystals contain distinctive CL zonings with a jagged ('restitic') core mantled by a black CL zone. Trace element variations in melt inclusions in the 'restitic' cores are consistent with fractionation of Ba-bearing minerals such as sanidine and/or biotite, both of which are rare or absent in rocks erupted from Taupo volcanic center. The above evidence suggests that Oruanui rhyolite is generated by assimilation of previous intruded rocks or country rocks, differentiated by crystal fractionation, and then mixed prior to eruption. Despite the differences in trace element and volatile contents, and crystal assemblages, both Bishop Tuff and Oruanui magmas involve crystal fractionation as one of the main differentiation mechanisms during their evolution. However, there are pronounced differences in the pre-eruptive stratification of the two chambers, which may reflect the tectonic settings, eruption rates, and ages of the systems.

Crystallization of Vocational Interests as a Function of Vocational Exploration in College

ERIC Educational Resources Information Center

Buck, Charles W.

1970-01-01

Scales of extensiveness and effectiveness were developed from a questionnaire administered immediately before graduation. Neither extensiveness nor effectiveness of reported vocational exploratory behavior were found to be significantly related to the level of final interest crystallization. (Author)

Elemental composition of the Martian crust.

PubMed

McSween, Harry Y; Taylor, G Jeffrey; Wyatt, Michael B

2009-05-08

The composition of Mars' crust records the planet's integrated geologic history and provides clues to its differentiation. Spacecraft and meteorite data now provide a global view of the chemistry of the igneous crust that can be used to assess this history. Surface rocks on Mars are dominantly tholeiitic basalts formed by extensive partial melting and are not highly weathered. Siliceous or calc-alkaline rocks produced by melting and/or fractional crystallization of hydrated, recycled mantle sources, and silica-poor rocks produced by limited melting of alkali-rich mantle sources, are uncommon or absent. Spacecraft data suggest that martian meteorites are not representative of older, more voluminous crust and prompt questions about their use in defining diagnostic geochemical characteristics and in constraining mantle compositional models for Mars.

Phase behavior of binary and polydisperse suspensions of compressible microgels controlled by selective particle deswelling

NASA Astrophysics Data System (ADS)

Scotti, A.; Gasser, U.; Herman, E. S.; Han, Jun; Menzel, A.; Lyon, L. A.; Fernandez-Nieves, A.

2017-09-01

We investigate the phase behavior of suspensions of poly(N -isopropylacrylamide) (pNIPAM) microgels with either bimodal or polydisperse size distribution. We observe a shift of the fluid-crystal transition to higher concentrations depending on the polydispersity or the fraction of large particles in suspension. Crystallization is observed up to polydispersities as high as 18.5%, and up to a number fraction of large particles of 29% in bidisperse suspensions. The crystal structure is random hexagonal close-packed as in monodisperse pNIPAM microgel suspensions. We explain our experimental results by considering the effect of bound counterions. Above a critical particle concentration, these cause deswelling of the largest microgels, which are the softest, changing the size distribution of the suspension and enabling crystal formation in conditions where incompressible particles would not crystallize.

Crystallization of the Pulsating White Dwarf Star, BPM 37093

NASA Astrophysics Data System (ADS)

Salois, Amee; Winget, D.

2010-01-01

BPM 37093 is unique among pulsating white dwarf stars because it is expected to have a highly crystallized interior. By understanding how this star is crystallizing, we gain a better understanding of extreme physics. Theoretical models of the evolution of white dwarf stars suggest that they crystallize from the inside out. The pulsations of the star, which we see as intensity variations, cannot penetrate this crystallized interior. Therefore, as the star crystallizes there is a smaller volume for the propagation of the pulsations and the pulsation periods are changed accordingly. We studied these changes in the periods of the pulsations of the star over ten weeks during the McDonald Observatory Research Experience for Undergraduates Program. By studying the changes in the pulsations periods of the star we can determine the mass fraction of the star that is crystallized. Comparing Fourier transforms of our observed light curves taken in 2004 and 2005 at CTIO with data taken in 1998 and 1999 by Kanaan et al. we hope to see the changes that have occurred in the star as well as determining a better approximation of the star's crystallized mass fraction.

Effect of crystal length on the thermal characteristic in Nd: YLF laser with 20W diode pumped

NASA Astrophysics Data System (ADS)

Yahya, K. A.; Hussein, O. A.; Mustafa, O. H.

2016-03-01

Theoretical results are reported on thermal effects along the π- 1047nm and σ- 1053nm polarizations in a cut Nd: YLF rod crystal by using 20W Diode -End-pumped. The crystal length effects on the fraction of absorbed pump radiation converted into heat, radial temperature distribution, and the change in a radial refractive index. The result from this study has shown that a maximum fraction converted into heat is calculated to be around 24% and thermal effects of π-polarized 1047 nm stronger than σ-polarized 1053 nm.

Petrogenesis of Neoarchean metavolcanic rocks in Changyukou, Northwestern Hebei: Implications for the transition stage from a compressional to an extensional regime for the North China Craton

NASA Astrophysics Data System (ADS)

Liou, Peng; Shan, Houxiang; Liu, Fu; Guo, Jinghui

2017-03-01

The 2.5 Ga metavolcanic rocks in Changyukou, Northwestern Hebei, can be classified into three groups based on major and trace elements: high-Mg basalts, tholeiitic basalts, and the calc-alkaline series (basaltic andesites-andesites and dacites-rhyolites). Both high-Mg basalts and tholeiitic basalts have negative anomalies of Nb, Zr, Ti and Heavy Rare Earth Elements (HREE) as well as enrichments of Sr, K, Pb, Ba and Light Rare Earth Elements (LREE) and show typical subduction zone affinities. The petrogenesis of high-Mg basalts can be ascribed to high-degree partial melting of an enriched mantle source in the spinel stability field that was previously enriched in Large Ion Lithophile Elements (LILE) and LREE by slab-derived hydrous fluids/melts/supercritical fluids, as well as the subsequent magma mixing processes of different sources at different source depths, with little or no influence of polybaric fractional crystallization. The flat HREE of tholeiitic basalts indicates they may also originate from the spinel stability field, but from obviously shallower depths than the source of high-Mg basalts. They may form at a later stage of the subduction process when rapid slab rollback leads to extension and seafloor spreading in the upper plate. We obtain the compositions of the Archean lower crust of the North China Craton based on the Archean Wutai-Jining section by compiling the average tonalite-trondhjemite-granodiorite (TTG) components, average mafic granulite components, and average sedimentary rock components. The modeling results show that the generation of high-Al basalts, basaltic andesites and andesites can be attributed to assimilation by high-Mg basalts (primary basalts) of relatively high-Al2O3 thickened lower crust and the subsequent crystallization of prevailing mafic mineral phases, while Al2O3-rich plagioclase crystallization is suppressed under high-pressure and nearly water-saturated conditions. Dacites and rhyolites may be the result of further fractional crystallization of basaltic andesites (high-Al basalts) and andesites. Mixing of magmas at various stages along the fractionation course of basaltic andesites (high-Al basalts) toward rhyolites promotes the trend of the calc-alkaline series. To reconcile the 2.55 to 2.5 Ga TTGs derived from overthickened crust, the 2.51 to 2.50 Ga calc-alkaline volcanic rocks derived from thickened crust, tholeiitic basalts representing low pressure and an extensional tectonic setting, 2493 Ma leucosyenogranites derived from overthickened crust, 2437 Ma biotite-monzogranites derived from slightly thinner crust than leucosyenogranites but still thickened, as well as the clockwise hybrid ITD and IBC P-T paths of the HP granulites and widespread extension and rifting setting within the NCC from 2300 Ma, we propose a model of an evolving subduction process. Among them, the composition of the 2.5 Ga Changyukou volcanic rocks and potassic granites as well as the clockwise hybrid ITD and IBC P-T paths of the HP granulites may reveal that the tectonic setting in Northwest Hebei was in a transition stage from a subduction-related compressional regime to an extensional regime related to plate rollback.

Filling constraints for spin-orbit coupled insulators in symmorphic and nonsymmorphic crystals

PubMed Central

Watanabe, Haruki; Po, Hoi Chun; Vishwanath, Ashvin; Zaletel, Michael

2015-01-01

We determine conditions on the filling of electrons in a crystalline lattice to obtain the equivalent of a band insulator—a gapped insulator with neither symmetry breaking nor fractionalized excitations. We allow for strong interactions, which precludes a free particle description. Previous approaches that extend the Lieb–Schultz–Mattis argument invoked spin conservation in an essential way and cannot be applied to the physically interesting case of spin-orbit coupled systems. Here we introduce two approaches: The first one is an entanglement-based scheme, and the second one studies the system on an appropriate flat “Bieberbach” manifold to obtain the filling conditions for all 230 space groups. These approaches assume only time reversal rather than spin rotation invariance. The results depend crucially on whether the crystal symmetry is symmorphic. Our results clarify when one may infer the existence of an exotic ground state based on the absence of order, and we point out applications to experimentally realized materials. Extensions to new situations involving purely spin models are also mentioned. PMID:26604304

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

Szcześ, Aleksandra, E-mail: aszczes@poczta.umcs.lublin.pl; Czemierska, Magdalena; Jarosz-Wilkołazka, Anna

Extracellular polymeric substance (EPS) extracted from Rhodococcus opacus bacterial strain was used as a matrix for calcium carbonate precipitation using the vapour diffusion method. The total exopolymer and water-soluble exopolymer fraction of different concentrations were spread on the mica surface by the spin-coating method. The obtained layers were characterized using the atomic force microscopy measurement and XPS analysis. The effects of polymer concentration, initial pH of calcium chloride solution and precipitation time on the obtained crystals properties were investigated. Raman spectroscopy and scanning electron microscopy were used to characterize the precipitated minerals. It was found that the type of precipitatedmore » CaCO{sub 3} polymorph and the crystal size depend on the kind of EPS fraction. The obtained results indicates that the water soluble fraction favours vaterite dissolution and calcite growth, whereas the total EPS stabilizes vaterite and this effect is stronger at basic pH. It seems to be due to different contents of the functional group of EPS fractions. - Highlights: • CaCO{sub 3} crystal size and polymorph can be controlled by EPS substance obtained from R. opacus. • The water soluble fraction favours vaterite dissolution and calcite growth. • The total EPS stabilizes vaterite. • This effect is stronger at basic pH.« less

Extension of many-body theory and approximate density functionals to fractional charges and fractional spins.

PubMed

Yang, Weitao; Mori-Sánchez, Paula; Cohen, Aron J

2013-09-14

The exact conditions for density functionals and density matrix functionals in terms of fractional charges and fractional spins are known, and their violation in commonly used functionals has been shown to be the root of many major failures in practical applications. However, approximate functionals are designed for physical systems with integer charges and spins, not in terms of the fractional variables. Here we develop a general framework for extending approximate density functionals and many-electron theory to fractional-charge and fractional-spin systems. Our development allows for the fractional extension of any approximate theory that is a functional of G(0), the one-electron Green's function of the non-interacting reference system. The extension to fractional charge and fractional spin systems is based on the ensemble average of the basic variable, G(0). We demonstrate the fractional extension for the following theories: (1) any explicit functional of the one-electron density, such as the local density approximation and generalized gradient approximations; (2) any explicit functional of the one-electron density matrix of the non-interacting reference system, such as the exact exchange functional (or Hartree-Fock theory) and hybrid functionals; (3) many-body perturbation theory; and (4) random-phase approximations. A general rule for such an extension has also been derived through scaling the orbitals and should be useful for functionals where the link to the Green's function is not obvious. The development thus enables the examination of approximate theories against known exact conditions on the fractional variables and the analysis of their failures in chemical and physical applications in terms of violations of exact conditions of the energy functionals. The present work should facilitate the calculation of chemical potentials and fundamental bandgaps with approximate functionals and many-electron theories through the energy derivatives with respect to the fractional charge. It should play an important role in developing accurate approximate density functionals and many-body theory.

Site-specific equilibrium isotopic fractionation of oxygen, carbon and calcium in apatite

NASA Astrophysics Data System (ADS)

Aufort, Julie; Ségalen, Loïc; Gervais, Christel; Paulatto, Lorenzo; Blanchard, Marc; Balan, Etienne

2017-12-01

The stable isotope composition of biogenic apatite is an important geochemical marker that can record environmental parameters and is widely used to infer past climates, biomineralization processes, dietary preferences and habitat of vertebrates. In this study, theoretical equilibrium isotopic fractionation of oxygen, carbon and calcium in hydroxyapatite and carbonate-bearing hydroxyapatite is investigated using first-principles methods based on density-functional theory and compared to the theoretical isotopic fractionation properties of calcite, CO2 and H2O. Considering the variability of apatite crystal-chemistry, special attention is given to specific contributions of crystal sites to isotopic fractionation. Significant internal fractionation is calculated for oxygen and carbon isotopes in CO3 between the different structural sites occupied by carbonate groups in apatite (typically 7‰ for both 18O/16O and 13C/12C fractionation at 37 °C). Compared with calcite-water oxygen isotope fractionation, occurrence of A-type substitution in apatite structure, in addition to the main B-type substitution, could explain the larger temperature dependence of oxygen isotope fractionation measured at low temperature between carbonate in apatite and water. Theoretical internal fractionation of oxygen isotopes between carbonate and phosphate in B-type carbonated apatite (∼8‰ at 37 °C) is consistent with experimental values obtained from modern and well-preserved fossil bio-apatites. Concerning calcium, theoretical results suggest a small fractionation between apatite and calcite (-0.17‰ at 37 °C). Internal fractionation reaching 0.8‰ at 37 °C occurs between the two Ca sites in hydroxyapatite. Furthermore, the Ca isotopic fractionation properties of apatite are affected by the occurrence of carbonate groups, which could contribute to the variability observed on natural samples. Owing to the complexity of apatite crystal-chemistry and in light of the theoretical results, measurements of site-specific isotopic fractionation properties could improve our understanding and the interpretation of isotopic records in apatites.

Isolation of isoelectrically pure cholera toxin for crystallization

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

Spangler, B.D.; Westbrook, E.M.

1989-01-01

We have determined that the failure of cholera toxin to crystallize well results from its isoelectric heterogeneity, which is probably due to a post-translational process such as deamidation of its B subunit. Every sample of cholera toxin we have examined from commercial or academic suppliers has been heterogeneous; heterogeneous cholera toxin does not crystallize satisfactorily. We have overcome this problem by using ion-exchange fast protein liquid chromatography (FPLC) to obtain an isoelectrically homogeneous species of cholera toxin. Homogeneous cholera toxin crystallizes readily, forming single, nonmosaic crystals suitable for x-ray diffraction studies. For this process, protein was applied to a MonoQmore » ion-exchange column, then eluted with an isocratic low salt buffer followed by a linear salt gradient (0-100 mM NaCl). Column fractions were analyzed on isoelectric focusing gels, and those fractions containing the desired homogeneous species were pooled and concentrated. Crystals formed within 24 to 48 hours in a MOPS/PEG buffer, which made use of slow isoelectric precipitation to induce crystallization. 23 refs., 6 figs.« less

Resonant coherent excitation of 390 MeV/u Ar ions planar channeled in Si crystals

NASA Astrophysics Data System (ADS)

Komaki, K.; Azuma, T.; Ito, T.; Takabayashi, Y.; Yamazaki, Y.; Sano, M.; Torikoshi, M.; Kitagawa, A.; Takada, E.; Murakami, T.

1998-12-01

Resonant coherent excitation of the 1s electron to n=2 states in a hydrogen-like ion was studied through measurements of the survived fraction of 390 MeV/u Ar17+ planar channeled in a Si crystal. Adopting a totally depleted Si surface barrier detector as a target crystal, the charge state of the individual emerged ion was measured in coincidence with the energy deposition in the target. By changing the incident direction along the (2 overline2 0), (0 0 4), and (1 overline1 1) planes, a series of clear resonances were observed as the decrease in the survived charge fraction due to higher electron loss probability for the excited state. Each resonance profile reflects energy splitting of the n=2 manifold originated from l-s interaction and Stark effect due to the crystal field. From the correlation between the energy loss and survived charge fraction, transition energy as a function of the ion trajectory amplitude is deduced which is in good agreement with calculated results.

Microstructure and Electrochemical Behavior of Fe-Based Amorphous Metallic Coatings Fabricated by Atmospheric Plasma Spraying

NASA Astrophysics Data System (ADS)

Zhou, Z.; Wang, L.; He, D. Y.; Wang, F. C.; Liu, Y. B.

2011-01-01

A Fe48Cr15Mo14C15B6Y2 alloy with high glass forming ability (GFA) was selected to prepare amorphous metallic coatings by atmospheric plasma spraying (APS). The as-deposited coatings present a dense layered structure and low porosity. Microstructural studies show that some nanocrystals and a fraction of yttrium oxides formed during spraying, which induced the amorphous fraction of the coatings decreasing to 69% compared with amorphous alloy ribbons of the same component. High thermal stability enables the amorphous coatings to work below 910 K without crystallization. The results of electrochemical measurement show that the coatings exhibit extremely wide passive region and relatively low passive current density in 3.5% NaCl and 1 mol/L HCl solutions, which illustrate their superior ability to resist localized corrosion. Moreover, the corrosion behavior of the amorphous coatings in 1 mol/L H2SO4 solution is similar to their performance under conditions containing chloride ions, which manifests their flexible and extensive ability to withstand aggressive environments.

Drilling into Magma: Experiences at Kīlauea Iki Lava Lake, Hawaii

NASA Astrophysics Data System (ADS)

Helz, R. L.

2017-12-01

Several historic lava lakes (1959 Kīlauea Iki, 1963 Alae, and 1965 Makaopuhi) were drilled in the 20th century, and molten core recovered from them. Kīlauea Iki lava lake, the most extensively studied, was drilled in 1960-62, 1967, 1965, 1976, 1979, 1981 and 1988. A total of 1400 m feet of core was recovered, about 210 m of which was partially molten. The melt fraction varied from near zero to 40-45% by volume, with higher fractions in glassy ooze from below the crust/melt interface. Most of the 1960-1979 drill holes terminated in pre-existing melt-rich internal differentiates; the later (1981, 1988) drill holes were mostly stopped arbitrarily. When melt was reached and the string backed off to wireline the last interval of core, black glassy ooze immediately moved up the borehole. Repeated re-entry and ooze recovery never exhausted the melt-rich sources. The first deep hole that did not hit melt was KI79-1, which was stopped at 62.2 m after recovering 12 m of molten mush. Here the uncased drill hole backfilled not with black glassy ooze but with olivine-rich, partly crystalline mush. The first redrilled core (recovered between 50.8 and 53.9 m), which moved up over a period of 16 days after termination of the original hole, underwent extensive separation of melt from crystals as it flowed upward. After this interval was pulled, drilling resumed with the bottom of the hole at 52.9 m, and uniform olivine-rich mush was recovered from 52.9-54.25 m. Drilling resumed once more at 52.9 m and a further 3 m of ooze recovered. The bit reached a depth of 55.4 m when the core barrel was full, suggesting that the crystal-rich mush was rising into the core barrel spontaneously during drilling. The three cores recovered in reentering KI79-1 show the effect of unloading the confining pressure on mush layers, with melt moving toward the low-pressure area (the bottom of the hole) relative to crystals. All of the crystal-rich mushes are more melt-rich than the original core, with elevated TiO2, K2O and P2O5 levels at the same bulk MgO content. Grain-to-grain contacts were progressively eroded in the melt-inflated mushes, so that the mushes had no internal cohesion. Although their melt contents never reached 50% by volume, they were extremely mobile, rising into the drill hole in minutes rather than the days required for the initial backfilling of the hole.

Bingham fluid behavior of plagioclase-bearing basaltic magma: Approach from laboratory viscosity measurements

NASA Astrophysics Data System (ADS)

Ishibashi, H.; Sato, H.

2010-12-01

Datasets of one atmosphere high temperature rotational viscometry of the Fuji 1707 basalt (Ishibashi, 2009) were analyzed based on the Bingham fluid model, and both yield stress and Bingham viscosity were determined. Reproducibility of the dataset by the Bingham fluid model was slightly better than that by the power law fluid modes adopted in our previous study although both the fluid models well represent the dataset in practical perspective. The relation between Bingham viscosity and crystallinity was compared with the Krieger-Dougherty equation, and both the maximum packing fraction of crystals and intrinsic viscosity for Bingham viscosity were determined ca. 0.45 and ca. 5.25, respectively, revealing that the maximum packing fraction decreased and intrinsic viscosity increased concomitantly with the increase in shape-anisotropy of crystals. However, the obtained value of the product of the maximum packing fraction and intrinsic viscosity (= ca. 2.36) was similar to that of uniform, isotropic-shaped particles (= 2.5), indicating that the effect of crystal shape-anisotropy on Bingham viscosity might be predicted only by change of the maximum packing fraction. Finite yield stress was detected for crystallinity larger than 0.133; it increased with crystallinity which suggests that critical crystallinity for onset of yield stress is at least lower than 0.133. The upper limit value of the critical crystallinity resembles the value calculated numerically for randomly oriented uniform particles by Saar et al. (2001) (0.10-0.15 for width/length ratio of 0.1-0.2, which is similar to the ratios in the basalt) whereas crystals in the basalt were moderately parallel arranged and their sizes vary significantly. That fact might be explained as follows; effects of parallel arrangement and size variation of crystals on the critical crystallinity are offset by the effect of variation in crystal shape-anisotropy, which suggests that shape-anisotropy distribution of crystals must be a critical factor for the onset of yield stress. Keywords: magma, viscosity, Bingham fluid, yield stress, plagioclase

Using cryoEM Reconstruction and Phase Extension to Determine Crystal Structure of Bacteriophage $${\\Phi}$$6 Major Capsid Protein

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

Nemecek, Daniel; Plevka, Pavel; Boura, Evzen

2013-11-29

Bacteriophagemore » $${\\Phi}$$6 is a double-stranded RNA virus that has been extensively studied as a model organism. In this paper we describe structure determination of $${\\Phi}$$6 major capsid protein P1. The protein crystallized in base centered orthorhombic space group C2221. Matthews’s coefficient indicated that the crystals contain from four to seven P1 subunits in the crystallographic asymmetric unit. The self-rotation function had shown presence of fivefold axes of non-crystallographic symmetry in the crystals. Thus, electron density map corresponding to a P1 pentamer was excised from a previously determined cryoEM reconstruction of the $${\\Phi}$$6 procapsid at 7 Å resolution and used as a model for molecular replacement. The phases for reflections at higher than 7 Å resolution were obtained by phase extension employing the fivefold non-crystallographic symmetry present in the crystal. Lastly, the averaged 3.6 Å-resolution electron density map was of sufficient quality to allow model building.« less

Self-Consistency of the Lauritzen-Hoffman and Strobl Models of Polymer Crystallization Evaluated for Poly(epsilon-caprolactone) Fractions and Effect of Composition on the Phenomenon of Concurrent Crystallization in Polyethylene Blends

NASA Astrophysics Data System (ADS)

Sheth, Swapnil Suhas

Narrow molecular weight fractions of poly(epsilon-caprolactone) were successfully obtained using the successive precipitation fractionation technique with toluene/n-heptane as a solvent/nonsolvent pair. Calorimetric studies of the melting behavior of fractions that were crystallized either isothermally or under constant cooling rate conditions suggested that the isothermal crystallization of the samples should be used for a proper evaluation of the molecular weight dependence of the observed melting temperature and degree of crystallinity in PCL. The molecular weight and temperature dependence of the spherulitic growth rate of fractions was studied in the context of the Lauritzen-Hoffman two-phase model and the Strobl three-phase model of polymer crystallization. The zero-growth rate temperatures, determined from spherulitic growth rates using four different methods, are consistent with each other and increase with chain length. The concomitant increase in the apparent secondary nucleation constant was attributed to two factors. First, for longer chains there is an increase in the probability that crystalline stems belong to loose chain-folds, hence, an increase in fold surface free energy. It is speculated that the increase in loose folding and resulting decrease in crystallinity with increasing chain length are associated with the ester group registration requirement in PCL crystals. The second contribution to the apparent nucleation constant arises from chain friction associated with segmental transport across the melt/crystal interface. These factors were responsible for the much stronger chain length dependence of spherulitic growth rates at fixed undercooling observed here with PCL than previously reported for PE and PEO. In the case of PCL, the scaling exponent associated with the chain length dependence of spherulitic growth rates exceeds the upper theoretical bound of 2 predicted from the Brochard- DeGennes chain pullout model. Observation that zero-growth and equilibrium melting temperature values are identical with each other within the uncertainty of their determinations casts serious doubt on the validity of Strobl three-phase model. A novel method is proposed to determine the Porod constant necessary to extrapolate the small angle X-ray scattering intensity data to large scattering vectors. The one-dimensional correlation function determined using this Porod constant yielded the values of lamellar crystal thickness, which were similar to these estimated using the Hosemann-Bagchi Paracrystalline Lattice model. The temperature dependence of the lamellar crystal thickness was consistent with both LH and the Strobl model of polymer crystallization. However, in contrast to the predictions of Strobl's model, the value of the mesomorph-to-crystal equilibrium transition temperature was very close to the zero-growth temperature. Moreover, the lateral block sizes (obtained using wide angle X-ray diffraction) and the lamellar thicknesses were not found to be controlled by the mesomorph-to-crystal equilibrium transition temperature. Hence, we concluded that the crystallization of PCL is not mediated by a mesophase. Metallocene-catalyzed linear low-density (m-LLDPE with 3.4 mol% 1-octene) and conventional low-density (LDPE) polyethylene blends of different compositions were investigated for their melt-state miscibility and concurrent crystallization tendency. Differential scanning calorimetric studies and morphological studies using atomic force microscopy confirm that these blends are miscible in the melt-state for all compositions. LDPE chains are found to crystallize concurrently with m-LLDPE chains during cooling in the m-LLDPE crystallization temperature range. While the extent of concurrent crystallization was found to be optimal in .. .. iv blends with highest m-LLDPE content studied, strong evidence was uncovered for the existence of a saturation effect in the concurrent crystallization behavior. This observation leads us to suggest that co-crystallization, rather than mere concurrent crystallization, of LDPE with m- LLDPE can indeed take place. Matching of the respective sequence length distributions in LDPE and m-LLDPE is suggested to control the extent of co-crystallization.

Early differentiation of the Moon: Experimental and modeling studies and experimental and modeling studies of massif anorthosites

NASA Technical Reports Server (NTRS)

Longhi, John

1994-01-01

NASA grant NAG9-329 was in effect from 3/1/89 to 8/31/94, the last 18 months being a no-cost extension. While the grant was in effect, the P.I., coworkers, and students gave 22 talks and poster sessions at professional meetings, published 12 articles in referred journals (one more is in press, and another is in review), and edited 2 workshop reports relevant to this project. Copies of all the publications are appended to this report. The major accomplishments during the grant period have derived from three quarters: 1) the application of quantitative models of fractional crystallization and partial melting to various problems in planetary science, such as the petrogenesis of picritic glasses and mare basalts and the implications of the SNC meteorites for martian evolution; 2) an experimental study of silicate liquid immiscibility relevant to early lunar differentiation and the petrogenesis of evolved highlands rocks; and 3) experimental studies of massif anorthosites and related rocks that provide terrestrial analogs for the proposed origin of lunar anorthosites by multistage processes. The low-pressure aspects of the quantitative models were developed by the P.I. in the 1980s with NASA support and culminated with a paper comparing the crystallization of terrestrial and lunar lavas. The basis for the high-pressure modifications to the quantitative models is a data set gleaned from high pressure melting experiments done at Lamont and is supplemented by published data from other labs that constrain the baric and compositional dependences of various liquidus phase boundaries such as olivine/orthopyroxene, relevant to the melting of the mantles of the terrestrial planets. With these models it is possible to predict not only the thermal and compositional evolution of magmatic liquids ranging in composition from lumar mare basalt to terrestrial calc-alkaline basalts, but also the small increments of fractional melting that are produced when mantle rises adiabatically. Copies of the crystallization/melting programs have been given to several colleagues in planetary science. Additionally, a series of computer graphics programs, based on the algorithms in the crystallization programs have been developed that display liquidus diagrams appropriate to input compositions.

A chemical model for generating the sources of mare basalts - Combined equilibrium and fractional crystallization of the lunar magmasphere

NASA Technical Reports Server (NTRS)

Snyder, Gregory A.; Taylor, Lawrence A.; Neal, Clive R.

1992-01-01

A chemical model for simulating the sources of the lunar mare basalts was developed by considering a modified mafic cumulate source formed during the combined equilibrium and fractional crystallization of a lunar magma ocean (LMO). The parameters which influence the initial LMO and its subsequent crystallization are examined, and both trace and major elements are modeled. It is shown that major elements tightly constrain the composition of mare basalt sources and the pathways to their creation. The ability of this LMO model to generate viable mare basalt source regions was tested through a case study involving the high-Ti basalts.

Numerical simulation of crystal fractionation in shergottite meteorites

NASA Astrophysics Data System (ADS)

Grimm, R. E.; McSween, H. Y., Jr.

Cumulus clinopyroxenes in the Shergotty and Zagami meteorites suggest crystal fractionation occurred, possibly by gravitative settling. Numerical models of this process in a nonconvecting environment argue that the small phenocrysts can segregate only under extreme conditions of cooling time or gravitational field strength. Since textures indicate that cooling time was not excessive, a large (planetary) g is required by these models, in agreement with other suggestions that the shergottite parent body may be Mars. Other calculations indicate that it is extremely difficult to produce the observed textures in a convecting environment, unless crystal setting occurred in a quiescent zone at the bottom of the magma chamber.

Numerical simulation of crystal fractionation in shergottite meteorites

NASA Technical Reports Server (NTRS)

Grimm, R. E.; Mcsween, H. Y., Jr.

1982-01-01

Cumulus clinopyroxenes in the Shergotty and Zagami meteorites suggest crystal fractionation occurred, possibly by gravitative settling. Numerical models of this process in a nonconvecting environment argue that the small phenocrysts can segregate only under extreme conditions of cooling time or gravitational field strength. Since textures indicate that cooling time was not excessive, a large (planetary) g is required by these models, in agreement with other suggestions that the shergottite parent body may be Mars. Other calculations indicate that it is extremely difficult to produce the observed textures in a convecting environment, unless crystal setting occurred in a quiescent zone at the bottom of the magma chamber.

Fractionation products of basaltic komatiite magmas at lower crustal pressures: implications for genesis of silicic magmas in the Archean

NASA Astrophysics Data System (ADS)

Mandler, B. E.; Grove, T. L.

2015-12-01

Hypotheses for the origin of crustal silicic magmas include both partial melting of basalts and fractional crystallization of mantle-derived melts[1]. Both are recognized as important processes in modern environments. When it comes to Archean rocks, however, partial melting hypotheses dominate the literature. Tonalite-trondhjemite-granodiorite (TTG)-type silicic magmas, ubiquitous in the Archean, are widely thought to be produced by partial melting of subducted, delaminated or otherwise deeply buried hydrated basalts[2]. The potential for a fractional crystallization origin for TTG-type magmas remains largely unexplored. To rectify this asymmetry in approaches to modern vs. ancient rocks, we have performed experiments at high pressures and temperatures to closely simulate fractional crystallization of a basaltic komatiite magma in the lowermost crust. These represent the first experimental determinations of the fractionation products of komatiite-type magmas at elevated pressures. The aim is to test the possibility of a genetic link between basaltic komatiites and TTGs, which are both magmas found predominantly in Archean terranes and less so in modern environments. We will present the 12-kbar fractionation paths of both Al-depleted and Al-undepleted basaltic komatiite magmas, and discuss their implications for the relative importance of magmatic fractionation vs. partial melting in producing more evolved, silicic magmas in the Archean. [1] Annen et al., J. Petrol., 47, 505-539, 2006. [2] Moyen J-F. & Martin H., Lithos, 148, 312-336, 2012.

Primary and secondary fragmentation of crystal-bearing intermediate magma

NASA Astrophysics Data System (ADS)

Jones, Thomas J.; McNamara, Keri; Eychenne, Julia; Rust, Alison C.; Cashman, Katharine V.; Scheu, Bettina; Edwards, Robyn

2016-11-01

Crystal-rich intermediate magmas are subjected to both primary and secondary fragmentation processes, each of which may produce texturally distinct tephra. Of particular interest for volcanic hazards is the extent to which each process contributes ash to volcanic plumes. One way to address this question is by fragmenting pyroclasts under controlled conditions. We fragmented pumice samples from Soufriere Hills Volcano (SHV), Montserrat, by three methods: rapid decompression in a shock tube-like apparatus, impact by a falling piston, and milling in a ball mill. Grain size distributions of the products reveal that all three mechanisms produce fractal breakage patterns, and that the fractal dimension increases from a minimum of 2.1 for decompression fragmentation (primary fragmentation) to a maximum of 2.7 by repeated impact (secondary fragmentation). To assess the details of the fragmentation process, we quantified the shape, texture and components of constituent ash particles. Ash shape analysis shows that the axial ratio increases during milling and that particle convexity increases with repeated impacts. We also quantify the extent to which the matrix is separated from the crystals, which shows that secondary processes efficiently remove adhering matrix from crystals, particularly during milling (abrasion). Furthermore, measurements of crystal size distributions before (using x-ray computed tomography) and after (by componentry of individual grain size classes) decompression-driven fragmentation show not only that crystals influence particular size fractions across the total grain size distribution, but also that free crystals are smaller in the fragmented material than in the original pumice clast. Taken together, our results confirm previous work showing both the control of initial texture on the primary fragmentation process and the contributions of secondary processes to ash formation. Critically, however, our extension of previous analyses to characterisation of shape, texture and componentry provides new analytical tools that can be used to assess contributions of secondary processes to ash deposits of uncertain or mixed origin. We illustrate this application with examples from SHV deposits.

Closed system oxygen isotope redistribution in igneous CAIs upon spinel dissolution

NASA Astrophysics Data System (ADS)

Aléon, Jérôme

2018-01-01

In several Calcium-Aluminum-rich Inclusions (CAIs) from the CV3 chondrites Allende and Efremovka, representative of the most common igneous CAI types (type A, type B and Fractionated with Unknown Nuclear isotopic anomalies, FUN), the relationship between 16O-excesses and TiO2 content in pyroxene indicates that the latter commonly begins to crystallize with a near-terrestrial 16O-poor composition and becomes 16O-enriched during crystallization, reaching a near-solar composition. Mass balance calculations were performed to investigate the contribution of spinel to this 16O-enrichment. It is found that a back-reaction of early-crystallized 16O-rich spinel with a silicate partial melt having undergone a 16O-depletion is consistent with the O isotopic evolution of CAI minerals during magmatic crystallization. Dissolution of spinel explains the O isotopic composition (16O-excess and extent of mass fractionation) of pyroxene as well as that of primary anorthite/dmisteinbergite and possibly that of the last melilite crystallizing immediately before pyroxene. It requires that igneous CAIs behaved as closed-systems relative to oxygen from nebular gas during a significant fraction of their cooling history, contrary to the common assumption that CAI partial melts constantly equilibrated with gas. The mineralogical control on O isotopes in igneous CAIs is thus simply explained by a single 16O-depletion during magmatic crystallization. This 16O-depletion occurred in an early stage of the thermal history, after the crystallization of spinel, i.e. in the temperature range for melilite crystallization/partial melting and did not require multiple, complex or late isotope exchange. More experimental work is however required to deduce the protoplanetary disk conditions associated with this 16O-depletion.

Gravity driven and in situ fractional crystallization processes in the Centre Hill complex, Abitibi Subprovince, Canada: Evidence from bilaterally-paired cyclic units

NASA Astrophysics Data System (ADS)

Thériault, R. D.; Fowler, A. D.

1996-12-01

The formation of layers in mafic intrusions has been explained by various processes, making it the subject of much controversy. The concept that layering originates from gravitational settling of crystals has been superseded in recent years by models involving in situ fractional crystallization. Here we present evidence from the Centre Hill complex that both processes may be operative simultaneously within the same intrusion. The Centre Hill complex is part of the Munro Lake sill, an Archean layered mafic intrusion emplaced in volcanic rocks of the Abitibi Subprovince. The Centre Hill complex comprises the following lithostratigraphic units: six lower cyclic units of peridotite and clinopyroxenite; a middle unit of leucogabbro; six upper cyclic units of branching-textured gabbro (BTG) and clotted-textured gabbro (CTG), the uppermost of these units being overlain by a marginal zone of fine-grained gabbro. The cyclic units of peridotite/clinopyroxenite and BTG/CTG are interpreted to have formed concurrently through fractional crystallization, associated with periodic replenishment of magma to the chamber. The units of peridotite and clinopyroxenite formed by gravitational accumulation of crystals that grew under the roof. The cyclic units of BTG and CTG formed along the upper margin of the sill by two different mechanisms: (1) layers of BTG crystallized in situ along an inward-growing roof and (2) layers of CTG formed by accumulation of buoyant plagioclase crystals. The layers of BTG are characterized by branching pseudomorphs after fayalite up to 50 cm in length that extend away from the upper margin. The original branching crystals are interpreted to have grown from stagnant intercumulus melt in a high thermal gradient resulting from the injection of new magma to the chamber.

Direct numerical simulations of magmatic differentiation at the microscopic scale

NASA Astrophysics Data System (ADS)

Sethian, J.; Suckale, J.; Elkins-Tanton, L. T.

2010-12-01

A key question in the context of magmatic differentiation and fractional crystallization is the ability of crystals to decouple from the ambient fluid and sink or rise. Field data indicates a complex spectrum of behavior ranging from rapid sedimentation to continued entrainment. Theoretical and laboratory studies paint a similarly rich picture. The goal of this study is to provide a detailed numerical assessment of the competing effects of sedimentation and entrainment at the scale of individual crystals. The decision to simulate magmatic differentiation at the grain scale comes at the price of not being able to simultaneously solve for the convective velocity field at the macroscopic scale, but has the crucial advantage of enabling us to fully resolve the dynamics of the systems from first principles without requiring any simplifying assumptions. The numerical approach used in this study is a customized computational methodology developed specifically for simulations of solid-fluid coupling in geophysical systems. The algorithm relies on a two-step projection scheme: In the first step, we solve the multiple-phase Navier-Stokes or Stokes equation in both domains. In the second step, we project the velocity field in the solid domain onto a rigid-body motion by enforcing that the deformation tensor in the respective domain is zero. This procedure is also used to enforce the no-slip boundary-condition on the solid-fluid interface. We have extensively validated and benchmarked the method. Our preliminary results indicate that, not unexpectedly, the competing effects of sedimentation and entrainment depend sensitively on the size distribution of the crystals, the aspect ratio of individual crystals and the vigor of the ambient flow field. We provide a detailed scaling analysis and quantify our results in terms of the relevant non-dimensional numbers.

The temperature of the Icelandic mantle from olivine-spinel aluminum exchange thermometry

NASA Astrophysics Data System (ADS)

Matthews, S.; Shorttle, O.; Maclennan, J.

2016-11-01

New crystallization temperatures for four eruptions from the Northern Volcanic Zone of Iceland are determined using olivine-spinel aluminum exchange thermometry. Differences in the olivine crystallization temperatures between these eruptions are consistent with variable extents of cooling during fractional crystallization. However, the crystallization temperatures for Iceland are systematically offset to higher temperatures than equivalent olivine-spinel aluminum exchange crystallization temperatures published for MORB, an effect that cannot be explained by fractional crystallization. The highest observed crystallization temperature in Iceland is 1399 ± 20°C. In order to convert crystallization temperatures to mantle potential temperature, we developed a model of multilithology mantle melting that tracks the thermal evolution of the mantle during isentropic decompression melting. With this model, we explore the controls on the temperature at which primary melts begin to crystallize, as a function of source composition and the depth from which the magmas are derived. Large differences (200°C) in crystallization temperature can be generated by variations in mantle lithology, a magma's inferred depth of origin, and its thermal history. Combining this model with independent constraints on the magma volume flux and the effect of lithological heterogeneity on melt production, restricted regions of potential temperature-lithology space can be identified as consistent with the observed crystallization temperatures. Mantle potential temperature is constrained to be 1480-30+37 °C for Iceland and 1318-32+44 °C for MORB.

Magma differentiation rates from ( 226Ra / 230Th) and the size and power output of magma chambers

NASA Astrophysics Data System (ADS)

Blake, Stephen; Rogers, Nick

2005-08-01

We present a mathematical model for the evolution of the ( 226Ra / 230Th) activity ratio during simultaneous fractional crystallization and ageing of magma. The model is applied to published data for four volcanic suites that are independently known to have evolved by fractional crystallization. These are tholeiitic basalt from Ardoukoba, Djibouti, MORB from the East Pacific Rise, alkali basalt to mugearite from Vestmannaeyjar, Iceland, and basaltic andesites from Miyakejima, Izu-Bonin arc. In all cases ( 226Ra / 230Th) correlates with indices of fractional crystallization, such as Th, and the data fall close to model curves of constant fractional crystallization rate. The best fit rates vary from 2 to 6 × 10 - 4 yr - 1 . Consequently, the time required to generate moderately evolved magmas ( F ≤ 0.7) is of the order of 500 to 1500 yrs and closed magma chambers will have lifetimes of 1700 to 5000 yrs. These rates and timescales are argued to depend principally on the specific power output (i.e., power output per unit volume) of the magma chambers that are the sites of fractional crystallization. Equating the heat flux at the EPR to the heat flux from the sub-axial magma chamber that evolves at a rate of ca. 3 × 10 - 4 yr - 1 implies that the magma body is a sill of ca. 100 m thickness, a value which coincides with independent estimates from seismology. The similarity of the four inferred differentiation rates suggests that the specific power output of shallow magma chambers in a range of tectonic settings covers a similarly narrow range of ca. 10 to 50 MW km - 3 . Their differentiation rates are some two orders of magnitude slower than that of the basaltic Makaopuhi lava lake, Hawaii, that cooled to the atmosphere. This is consistent with the two orders of magnitude difference in heat flux between Makaopuhi and the East Pacific Rise. ( 226Ra / 230Th) data for magma suites related by fractional crystallization allow the magma differentiation rate to be estimated and, from this, the thermal budget of the magma chamber addressed, and where an independent measurement of heat flux exists, to place constraints on the size of the magma chamber. Such results have the potential to constrain the likely timescale and size of future eruptions of evolved magmas.

Evolution of Volcano-Plutonic Centers in the Northern Colorado River Extensional Corridor, Nevada-Arizona: Protracted Cycles of Replenishment, Mush Accumulation, Fractionation, and Melt Extraction

NASA Astrophysics Data System (ADS)

Miller, C. F.; Miller, J. S.; Claiborne, L. L.; Walker, B. A.; Faulds, J. E.; Wooden, J. L.

2007-12-01

Three major magmatic systems were simultaneously active during early development of the northern Colorado River extensional corridor. These systems, centered on Spirit Mountain batholith, Searchlight pluton, and Aztec Wash and Nelson plutons, include hypabyssal intrusions as well as coarser, deeper-seated rocks emplaced at depths of 5-13 km. Erupted products of Searchlight are clearly exposed; connections between the other systems and extensive coeval volcanic sequences, while very likely, remain unverified. Intrusion at each center began at 17-18 Ma and terminated with a dike swarm at ca. 15.5 Ma. Dikes, sills, and evidence for mingling document the frequent replenishment suggested by longevity of the centers. Quenched magmas in pillows, dikes, and chilled margins indicate that input included trachybasalt (49- 52 wt pct SiO2), trachydacite (quartz monzonite; 62-65 wt pct SiO2), and low-Si rhyolite (granite; ca. 73 wt pct SiO2); similar magmas formed a large part of the regional volcanic sequence. Some of the basalt may represent juvenile magma from enriched mantle, but Sr and Nd isotopic data indicate that all other input magmas are hybrids with both juvenile and ancient crustal components. Although local mixing is evident from field and geochemical evidence, the system-wide hybridization occurred at deeper crustal levels prior to emplacement into the upper crust. Whole-rock elemental compositions, field relations, crystal-size distributions and textures within the volcanic rocks and co-genetic intrusions indicate repeated cycles of magma emplacement and extraction of fractionated melt from cumulate mush. Cumulates are enriched in Sr and Ba and have positive Eu anomalies relative to input magmas. The melt-rich extracts have high-silica rhyolite compositions. They are exposed in plutons as small dikes and large subhorizontal sheets and roof zones comprising fine-grained, commonly vesicle-rich aplitic granite, and they erupted from the Searchlight center and probably from the others. These rocks are extremely depleted in Sr, Ba, and Eu, and middle REE, low in light REE, P, Ti, and Zr, and enriched in Rb, reflecting fractionation of feldspars and accessory minerals. Their high SiO2 (77-79 wt pct) attests to fractionation at shallow levels, consistent with emplacement depths of the upper parts of the plutons. SHRIMP U-Pb ages and compositional zoning in zircon also indicate repeated cycles of growth from fractionating melts and recycling into less evolved melts. Most samples have two or more distinguishable age populations, and many individual grains show evidence for resorption. Compositions of zones indicate that grains experienced dramatic temperature fluctuations and were transferred from highly fractionated to unfractionated melts. Taken together, these data indicate that the intrusions formed and were modified by repeated (a) felsic replenishment that eventually formed thick crystal mush; (b) mafic replenishments that helped to maintain a thermal balance; (c) extraction of fractionated melt into local conduits or ponding zones, to the roof, or to erupt at the surface; (d) rejuvenation of the mush by the preceding processes, entraining and transporting crystals and blurring previous intrusive contacts.

Atomistic model of the spider silk nanostructure

NASA Astrophysics Data System (ADS)

Keten, Sinan; Buehler, Markus J.

2010-04-01

Spider silk is an ultrastrong and extensible self-assembling biopolymer that outperforms the mechanical characteristics of many synthetic materials including steel. Here we report atomic-level structures that represent aggregates of MaSp1 proteins from the N. Clavipes silk sequence based on a bottom-up computational approach using replica exchange molecular dynamics. We discover that poly-alanine regions predominantly form distinct and orderly beta-sheet crystal domains while disorderly structures are formed by poly-glycine repeats, resembling 31-helices. These could be the molecular source of the large semicrystalline fraction observed in silks, and also form the basis of the so-called "prestretched" molecular configuration. Our structures are validated against experimental data based on dihedral angle pair calculations presented in Ramachandran plots, alpha-carbon atomic distances, as well as secondary structure content.

{Γ}-Convergence Analysis of a Generalized XY Model: Fractional Vortices and String Defects

NASA Astrophysics Data System (ADS)

Badal, Rufat; Cicalese, Marco; De Luca, Lucia; Ponsiglione, Marcello

2018-03-01

We propose and analyze a generalized two dimensional XY model, whose interaction potential has n weighted wells, describing corresponding symmetries of the system. As the lattice spacing vanishes, we derive by {Γ}-convergence the discrete-to-continuum limit of this model. In the energy regime we deal with, the asymptotic ground states exhibit fractional vortices, connected by string defects. The {Γ}-limit takes into account both contributions, through a renormalized energy, depending on the configuration of fractional vortices, and a surface energy, proportional to the length of the strings. Our model describes in a simple way several topological singularities arising in Physics and Materials Science. Among them, disclinations and string defects in liquid crystals, fractional vortices and domain walls in micromagnetics, partial dislocations and stacking faults in crystal plasticity.

Studies of quaternary saline lakes-I. Hydrogen isotope fractionation in saline minerals

USGS Publications Warehouse

Matsuo, S.; Friedman, I.; Smith, G.I.

1972-01-01

Borax, gaylussite, nahcolite and trona were synthesized in aqueous solution at temperatures ranging from 8?? to 35??C. Except for borax, deuterium was always depleted in these hydrated minerals relative to the solutions from which they were crystallized. In borax, no significant fractionation was found. The fractionation factor of D H for the trona-water system exhibited a marked temperature dependence. By combining the deuterium contents of trona and the solution from which trona was crystallized, the following thermometer scale was obtained: In ( D H) trona ( D H)water = 1.420 ?? 104 T2 + 23.56 T (1). An attempt to establish a geothermometer based on C13 C12 fractionation between carbonate minerals and carbonate ions in aqueous solution was not successful. ?? 1972.

Crystallization kinetics of orthorhombic paracetamol from supercooled melts studied by non-isothermal DSC.

PubMed

Nikolakakis, Ioannis; Kachrimanis, Kyriakos

2017-02-01

A simple and highly reproducible procedure was established for the study of orthorhombic paracetamol crystallization kinetics, comprising melting, quench-cooling of the melt and scanning the formed glass by DSC at different heating rates. Results were analyzed on the basis of the mean as well as local values of the Avrami exponent, n, the energy of activation, as well as the Šesták-Berggren two-parameter autocatalytic kinetic model. The mean value of the Avrami kinetic exponent, n, ranged between 3 and 5, indicating deviation from the nucleation and growth mechanism underlying the Johnson-Mehl, Avrami-Kolmogorov (JMAK) model. To verify the extent of the deviation, local values of the Avrami exponent as a function of the volume fraction transformed were calculated. Inspection of the local exponent values indicates that the crystallization mechanism changes over time, possibly reflecting the uncertainty of crystallization onset, instability of nucleation due to an autocatalytic effect of the crystalline phase, and growth anisotropy due to impingement of spherulites in the last stages of crystallization. The apparent energy of activation, E a , has a rather low mean value, close to 81 kJ/mol, which is in agreement with the observed instability of glassy-state paracetamol. Isoconversional methods revealed that E a tends to decrease with the volume fraction transformed, possibly because of the different energy demands of nucleation and growth. The exponents of the Šesták-Berggren two-parameter model showed that the crystallized fraction influences the process, confirming the complexity of the crystallization mechanism.

A-type granite and the Red Sea opening

USGS Publications Warehouse

Coleman, R.G.; DeBari, S.; Peterman, Z.

1992-01-01

Miocene-Oligocene A-type granite intrudes the eastern side of the Red Sea margin within the zone of extension from Jiddah, Saudi Arabia south to Yemen. The intrusions developed in the early stages of continental extension as Arabia began to move slowly away from Africa (around 30-20 Ma). Within the narrow zone of extension silicic magmas formed dikes, sills, small plutons and extrusive equivalents. In the Jabal Tirf area of Saudi Arabia these rocks occur in an elongate zone consisting of late Precambrian basement to the east, which is gradually invaded by mafic dikes. The number of dikes increases westward until an igneous complex is produced parallel to the present Red Sea axis. The Jabal Tirf igneous complex consists of diabase and rhyolite-granophyre sills (20-24 Ma). Although these are intrusine intrusive rocks their textures indicate shallow depths of intrusion (< 1 km). To the south, in the Yemen, contemporaneous with alkali basaltic eruptions (26-30 Ma) and later silicic eruptions, small plutons, dikes, and stocks of alkali granite invaded thick (1500 m) volcanic series, at various levels and times. Erosion within the uplifted margin of Yemen suggests that the maximum depth of intrusion was less than 1-2 km. Granophyric intrusions (20-30 Ma) within mafic dike swarms similar to the Jabal Tirf complex are present along the western edge of the Yemen volcanic plateau, marking a north-south zone of continental extension. The alkali granites of Yemen consist primarily of perthitic feldspar and quartz with some minor alkali amphiboles and acmite. These granites represent water-poor, hypersolvus magmas generated from parent alkali basalt magmas. The granophyric, two-feldspar granites associated with the mafic dike swarms and layered gabbros formed by fractional crystallization from tholeiitic basalt parent developed in the early stages of extension. Initial 87Sr/86Sr ratios of these rocks and their bulk chemistry indicate that production of peralkaline and metaluminous granitic magmas involved both fractio??nation and partial melting as they ascended through the late Precambrian crust of the Arabian plate. ?? 1992.

Partially deuterated potassium dihydrogen phosphate optimized for ultra-broadband optical parametric amplification

NASA Astrophysics Data System (ADS)

Fujioka, K.; Fujimoto, Y.; Tsubakimoto, K.; Kawanaka, J.; Shoji, I.; Miyanaga, N.

2015-03-01

The refractive index of a potassium dihydrogen phosphate (KDP) crystal strongly depends on the deuteration fraction of the crystal. The wavelength dependence of the phase-matching angle in the near-infrared optical parametric process shows convex and concave characteristics for pure KDP and pure deuterated KDP (DKDP), respectively, when pumped by the second harmonic of Nd- or Yb-doped solid state lasers. Using these characteristics, ultra-broadband phase matching can be realized by optimization of the deuteration fraction. The refractive index of DKDP that was grown with a different deuteration fraction (known as partially deuterated KDP or pDKDP) was measured over a wide wavelength range of 0.4-1.5 μm by the minimum deviation method. The wavelength dispersions of the measured refractive indices were fitted using a modified Sellmeier equation, and the deuteration fraction dependence was analyzed using the Lorentz-Lorenz equation. The wavelength-dependent phase-matching angle for an arbitrary deuteration fraction was then calculated for optical parametric amplification with pumping at a wavelength of 526.5 nm. The results revealed that a refractive index database with precision of more than 2 × 10-5 was necessary for exact evaluation of the phase-matching condition. An ultra-broad gain bandwidth of up to 490 nm will be feasible when using the 68% pDKDP crystal.

Non-3D domain swapped crystal structure of truncated zebrafish alphaA crystallin

PubMed Central

Laganowsky, A; Eisenberg, D

2010-01-01

In previous work on truncated alpha crystallins (Laganowsky et al., Protein Sci 2010; 19:1031–1043), we determined crystal structures of the alpha crystallin core, a seven beta-stranded immunoglobulin-like domain, with its conserved C-terminal extension. These extensions swap into neighboring cores forming oligomeric assemblies. The extension is palindromic in sequence, binding in either of two directions. Here, we report the crystal structure of a truncated alphaA crystallin (AAC) from zebrafish (Danio rerio) revealing C-terminal extensions in a non three-dimensional (3D) domain swapped, “closed” state. The extension is quasi-palindromic, bound within its own zebrafish core domain, lying in the opposite direction to that of bovine AAC, which is bound within an adjacent core domain (Laganowsky et al., Protein Sci 2010; 19:1031–1043). Our findings establish that the C-terminal extension of alpha crystallin proteins can be either 3D domain swapped or non-3D domain swapped. This duality provides another molecular mechanism for alpha crystallin proteins to maintain the polydispersity that is crucial for eye lens transparency. PMID:20669149

Disequilibrium dihedral angles in layered intrusions: the microstructural record of fractionation

NASA Astrophysics Data System (ADS)

Holness, Marian; Namur, Olivier; Cawthorn, Grant

2013-04-01

The dihedral angle formed at junctions between two plagioclase grains and a grain of augite is only rarely in textural equilibrium in gabbros from km-scale crustal layered intrusions. The median of a population of these disequilibrium angles, Θcpp, varies systematically within individual layered intrusions, remaining constant over large stretches of stratigraphy with significant increases or decreases associated with the addition or reduction respectively of the number of phases on the liquidus of the bulk magma. The step-wise changes in Θcpp are present in Upper Zone of the Bushveld Complex, the Megacyclic Unit I of the Sept Iles Intrusion, and the Layered Series of the Skaergaard Intrusion. The plagioclase-bearing cumulates of Rum have a bimodal distribution of Θcpp, dependent on whether the cumulus assemblage includes clinopyroxene. The presence of the step-wise changes is independent of the order of arrival of cumulus phases and of the composition of either the cumulus phases or the interstitial liquid inferred to be present in the crystal mush. Step-wise changes in the rate of change in enthalpy with temperature (ΔH) of the cooling and crystallizing magma correspond to the observed variation of Θcpp, with increases of both ΔH and Θcpp associated with the addition of another liquidus phase, and decreases of both associated with the removal of a liquidus phase. The replacement of one phase by another (e.g. olivine ⇔ orthpyroxene) has little effect on ΔH and no discernible effect on Θcpp. An increase of ΔH is manifest by an increase in the fraction of the total enthalpy budget that is the latent heat of crystallization (the fractional latent heat). It also results in an increase in the amount crystallized in each incremental temperature drop (the crystal productivity). An increased fractional latent heat and crystal productivity result in an increased rate of plagioclase growth compared to that of augite during the final stages of solidification, causing a step-wise increase in Θcpp. Step-wise changes in the geometry of three-grain junctions in fully solidified gabbros thus provide a clear microstructural marker for the progress of fractionation.

Reinvestigation of growth of 'L-valine zinc sulphate' crystal.

PubMed

Srinivasan, Bikshandarkoil R; Jyai, Rita N

2014-01-01

A reinvestigation of the growth of l-valine zinc sulphate crystal is reported. The slow evaporation of an aqueous solution containing l-valine and zinc sulphate heptahydrate results in the fractional crystallization of l-valine and not the organic inorganic hybrid nonlinear optical l-valine zinc sulphate crystal, as reported by Puhal Raj and Ramachandra Raja (2012). Copyright © 2013 Elsevier B.V. All rights reserved.

An Interactive Computer Program for Simulating the Effects of Olivine Fractionation from Basaltic and Ultrabasic Liquids.

ERIC Educational Resources Information Center

Pearce, Thomas H.

1983-01-01

Describes interactive computer program (listing available from author) which simulates olivine fractionation from basaltic/ultrabasic liquid. The menu-driven nature of the program (for Apple II microcomputer) allows students to select ideal Rayleigh fractionation or equilibrium crystallization. (JN)

Broadband sound blocking in phononic crystals with rotationally symmetric inclusions.

PubMed

Lee, Joong Seok; Yoo, Sungmin; Ahn, Young Kwan; Kim, Yoon Young

2015-09-01

This paper investigates the feasibility of broadband sound blocking with rotationally symmetric extensible inclusions introduced in phononic crystals. By varying the size of four equally shaped inclusions gradually, the phononic crystal experiences remarkable changes in its band-stop properties, such as shifting/widening of multiple Bragg bandgaps and evolution to resonance gaps. Necessary extensions of the inclusions to block sound effectively can be determined for given incident frequencies by evaluating power transmission characteristics. By arraying finite dissimilar unit cells, the resulting phononic crystal exhibits broadband sound blocking from combinational effects of multiple Bragg scattering and local resonances even with small-numbered cells.

Fractional calculus in hydrologic modeling: A numerical perspective

PubMed Central

Benson, David A.; Meerschaert, Mark M.; Revielle, Jordan

2013-01-01

Fractional derivatives can be viewed either as handy extensions of classical calculus or, more deeply, as mathematical operators defined by natural phenomena. This follows the view that the diffusion equation is defined as the governing equation of a Brownian motion. In this paper, we emphasize that fractional derivatives come from the governing equations of stable Lévy motion, and that fractional integration is the corresponding inverse operator. Fractional integration, and its multi-dimensional extensions derived in this way, are intimately tied to fractional Brownian (and Lévy) motions and noises. By following these general principles, we discuss the Eulerian and Lagrangian numerical solutions to fractional partial differential equations, and Eulerian methods for stochastic integrals. These numerical approximations illuminate the essential nature of the fractional calculus. PMID:23524449

Analyses of Cometary Silicate Crystals: DDA Spectral Modeling of Forsterite

NASA Technical Reports Server (NTRS)

Wooden, Diane

2012-01-01

Comets are the Solar System's deep freezers of gases, ices, and particulates that were present in the outer protoplanetary disk. Where comet nuclei accreted was so cold that CO ice (approximately 50K) and other supervolatile ices like ethane (C2H2) were preserved. However, comets also accreted high temperature minerals: silicate crystals that either condensed (greater than or equal to 1400 K) or that were annealed from amorphous (glassy) silicates (greater than 850-1000 K). By their rarity in the interstellar medium, cometary crystalline silicates are thought to be grains that formed in the inner disk and were then radially transported out to the cold and ice-rich regimes near Neptune. The questions that comets can potentially address are: How fast, how far, and over what duration were crystals that formed in the inner disk transported out to the comet-forming region(s)? In comets, the mass fractions of silicates that are crystalline, f_cryst, translate to benchmarks for protoplanetary disk radial transport models. The infamous comet Hale-Bopp has crystalline fractions of over 55%. The values for cometary crystalline mass fractions, however, are derived assuming that the mineralogy assessed for the submicron to micron-sized portion of the size distribution represents the compositional makeup of all larger grains in the coma. Models for fitting cometary SEDs make this assumption because models can only fit the observed features with submicron to micron-sized discrete crystals. On the other hand, larger (0.1-100 micrometer radii) porous grains composed of amorphous silicates and amorphous carbon can be easily computed with mixed medium theory wherein vacuum mixed into a spherical particle mimics a porous aggregate. If crystalline silicates are mixed in, the models completely fail to match the observations. Moreover, models for a size distribution of discrete crystalline forsterite grains commonly employs the CDE computational method for ellipsoidal platelets (c:a:b=8.14x8.14xl in shape with geometrical factors of x:y:z=1:1:10, Fabian et al. 2001; Harker et al. 2007). Alternatively, models for forsterite employ statistical methods like the Distribution of Hollow Spheres (Min et al. 2008; Oliveira et al. 2011) or Gaussian Random Spheres (GRS) or RGF (Gielen et al. 200S). Pancakes, hollow spheres, or GRS shapes similar to wheat sheaf crystal habit (e.g., Volten et al. 2001; Veihelmann et al. 2006), however, do not have the sharp edges, flat faces, and vertices seen in images of cometary crystals in interplanetary dust particles (IDPs) or in Stardust samples. Cometary forsterite crystals often have equant or tabular crystal habit (J. Bradley). To simulate cometary crystals, we have computed absorption efficiencies of forsterite using the Discrete Dipole Approximation (DDA) DDSCAT code on NAS supercomputers. We compute thermal models that employ a size distribution of discrete irregularly shaped forsterite crystals (nonspherical shapes with faces and vertices) to explore how crystal shape affects the shape and wavelength positions of the forsterite spectral features and to explore whether cometary crystal shapes support either condensation or annealing scenarios (Lindsay et al. 2012a, b). We find forsterite crystal shapes that best-fit comet Hale-Bopp are tetrahedron, bricks or brick platelets, essentially equant or tabular (Lindsay et al. 2012a,b), commensurate with high temperature condensation experiments (Kobatake et al. 2008). We also have computed porous aggregates with crystal monomers and find that the crystal resonances are amplified. i.e., the crystalline fraction is lower in the aggregate than is derived by fitting a linear mix of spectral features from discrete subcomponents, and the crystal resonances 'appear' to be from larger crystals (Wooden et al. 2012). These results may indicate that the crystalline mass fraction in comets with comae dominated by aggregates may be lower than deduced by popular methods that only emoy ensembles of discrete crystals.

Production of extreme-purity aluminum and silicon by fractional crystallization processing

NASA Astrophysics Data System (ADS)

Dawless, R. K.; Troup, R. L.; Meier, D. L.; Rohatgi, A.

1988-06-01

Large scale fractional crystallization is used commercially at Alcoa to produce extreme purity aluminum (99.999+% Al). The primary market is sputtering targets used to make interconnects for integrated circuits. For some applications the impurities uranium and thorium are reduced to less than 1 ppbw to avoid "soft errors" associated with α particle emission. The crystallization process achieves segregation coefficients which are close to theoretical at normal yields, and this, coupled with the scale of the units, allows practical production of this material. The silicon purification process involves crystallization of Si from molten aluminum alloys containing about 30% silicon. The crystallites from this process are further treated to remove residual Al and an extreme purity ingot is obtained. This material is considered suitable for single crystal or ribbon type photovoltaic cells and for certain IC applications, including highly doped substrates used for epitaxial growth. In production of both extreme purity Al and Si, impurities are rejected to the remaining melt as the crystals form and some separation is achieved by draining this downgraded melt from the unit. Purification of this downgrade by crystallization has also been demonstrated for both systems and is important for achieving high recoveries.

Thorium and uranium variations in Apollo 17 basalts, and K-U systematics

NASA Technical Reports Server (NTRS)

Laul, J. C.; Fruchter, J. S.

1976-01-01

It is found that Apollo 11 low-K and in particular Apollo 17 mare basalts show a wide range of Th/U ratios unlike other rocks; such variations cannot be explained by near surface crystal fractionation. A two-stage fractional crystallization-partial melting model involving a clinopyroxene cumulate as the major phase can explain the variations in Th/U ratios. Due to the Sm-Nd systematics constraint, several source cumulates are invoked to explain the observed Th/U continuum.

The study of the thermal behavior of a new semicrystalline polyimide

NASA Technical Reports Server (NTRS)

Cheng, Stephen Z. D.; Chalmers, Tammy M.

1992-01-01

Thermal properties of a new semicrystalline polyimide synthesized from 3,3',4,4' benzophenone tetracarboxylic dianhydride (BTDA) and 2,2 dimethyl 1,2-(4 aminophenoxy) propane (DMDA) were studied. Heat capacities in the solid and liquid states of BTDA-DMDA were measured. The heat capacity increase at the glass transition temperature (T sub g = 230 C) is 145 J/(C mol) for amorphous BTDA-DMDA. The equilibrium heat of fusion of the BTDA-DMDA crystals was obtained using wide angle X ray diffraction and differential scanning calorimetry measurements, and it is 75.8 kJ/mol. Based on the information of crystallinity and the heat capacity increase at T sub g, a rigid amorphous fraction is identified in semicrystalline BTDA-DMDA samples. The rigid amorphous fraction represents an interfacial region between the crystalline and amorphous states. In particular, this fraction increases with the crystallinity of the sample which should be associated with crystal sizes, and therefore, with crystal morphology. It was also found that this polymer has a high temperature crystal phase upon annealing above its original melting temperature. The thermal degradation activation energies are determined to be 154 and 150 kJ/mol in nitrogen and air, respectively.

Chain confinement, phase transitions, and lamellar structure in semicrystalline polymers, polymer blends and polymer nanocomposites

NASA Astrophysics Data System (ADS)

Chen, Huipeng

Recent studies suggest that there are three phase fractions in semicrystalline polymers, the crystalline, the mobile amorphous and the rigid amorphous phases. Due to the distinct properties of the rigid amorphous fraction, RAF, it has been investigated for more than twenty years. In this thesis, a general method using quasi-isothermal temperature-modulated differential scaning calorimetry, DSC, is provided for the first time to obtain the temperature dependent RAF and the other two fractions, crystalline fraction and mobile amorphous fraction, MAF. For poly(ethylene terephthalate), PET, our results show RAF was vitrified during quasi-isothermal cooling after crystallization had been completed and became totally devitrified during quasi-isothermal heating before the start of melting. Several years after people initially discovered the existence of RAF, another issue arose relating to the physical location of RAF and mobile amorphous fraction, MAF, within a lamellar stack model. Two very different models to describe the location of RAF were proposed. In the Heterogeneous Stack Model, HET, RAF is located outside the lamellar stacks. In the Homogeneous Stack Model, HSM, RAF was located inside the lamellar stacks. To determine the lamellar structure of semicrystalline polymers comprising three phase, a general method is given in this thesis by using a combination of the DSC and small angle X-ray scattering, SAXS techniques. It has been applied to Nylon 6, isotactic polystyrene, iPS, and PET. It was found for all of these materials, the HSM model is correct to describe the lamellar structure. In addition to the determination of lamellar structures, this method can also provide the exact fraction of MAF inside and outside lamellar stacks for binary polymer blends. For binary polymer blends, MAF, normally is located partially inside and partially outside the lamellar stacks. However, the quantification of the MAF inside and outside the lamellar stacks has now been provided and is applied to the iPS/atactic polystyrene, aPS, blends. The fractions of MAF inside and outside the lamellar stacks were quantified for the first time. For A/B binary polymer blends, it has been reported that if B is already crystalline, the crystalline fraction would serve as a restriction on the subsequent growth of the crystallizable partner A, while amorphous fraction could be diffused from the crystalline growth front of the crystallizing A component. Considering the effect of RAF on binary blends, a new concept is provided: like the crystals, the RAF of one polymer component may inhibit the growth of crystals of the other blend partner. The non-isothermal crystallization of PET/poly(lactic acid), PLA, blends were investigated and the results confirmed the new concept is correct: PET forms a large amount of RAF and inhibits crystal formation in PLA. Then, we broadened the concept of RAF and investigated the RAF in recent 'hot' materials, polymer nanocomposites. It was found the fraction of RAF greatly increased with a small amount of multi-wall carbon nanotubes, MWCNT, loading in PET electrospun, ES, fibers. A general model is given for polymer ES fibers with MWCNTs: the addition of MWCNTs causes polymer chains in the ES fibers to become more extended, (ie, more stretched), resulting in more confinement of PET chains and an increase in the RAF.

Using experimental petrology to constrain genesis of wet, silicic magmas in the Tonga-Kermadec island arc

NASA Astrophysics Data System (ADS)

Brens, R.; Rushmer, T. A.; Turner, S.; Adam, J.

2012-12-01

The Tongan arc system is comprised of a pair of island chains, where the western chain is the active volcanic arc. A range of rock suites, from basaltic andesites (53-56% SiO2) to dacites (64-66% SiO2), has been recovered from Late, Tofua and Fonualei in the Tonga-Kermadec primitive island arc system. For which the question arises: What is the mechanism that allows for silicic magmas to develop in a primitive island arc system? Caufield et al. (2012) suggest that fractional crystallization of a multi magma chamber process, with varying depth, is responsible for the silicic magma generation in this arc. Models such as this one have been proposed and experimentally tested in other systems (Novarupta, Alaska) to explain the origin of these silicic rocks. Our Tongan suite of rocks has had a full geochemical analysis for majors, traces and isotopes. The lavas from Tofua and Late are Fe-rich and have low concentrations of K, Rb, Ba, Zr, REE, Pb and U. However, experimental studies are needed to complement the extensive geochemical analysis done on the Tongan arc. Former geochemical work done on the igneous rocks from both of these volcanic suites from this arc suggests that the source of these rocks extend from 1.5-5.5 km in depth (Caulfield et al., 2012). Here, we present an experimental study of the phase equilibria on a natural andesitic sample (Late 1, from Ewart et al., 1975) from the island of Late. Experiments were run using the temperature constraints between 900 to 1220oC, pressure from 5 to 25 kbars and H2O addition of mostly 5wt% (but some results were obtained at 2wt% in the rocks). In the presence of 5 wt% water, phase equilibria of these experiments show the garnet stability field at >10 kb for 900 oC and increases with increasing temperature, while plagioclase enters at lower pressures when garnet exits. Experimental results currently suggests, at lower temperatures (900-950oC), a fractional crystallization relationship due to shallow level pressures of these rocks and further reinforcing Brophy's (2009) model of crystal fractionation of basalt to dacite in the presence of water, as an important process for which silica-rich magmas are produced within a primitive oceanic island arc.

Crystallization of a 2:2 complex of granulocyte-colony stimulating factor (GCSF) with the ligand-binding region of the GCSF receptor

PubMed Central

Honjo, Eijiro; Tamada, Taro; Maeda, Yoshitake; Koshiba, Takumi; Matsukura, Yasuko; Okamoto, Tomoyuki; Ishibashi, Matsujiro; Tokunaga, Masao; Kuroki, Ryota

2005-01-01

The granulocyte-colony stimulating factor (GCSF) receptor receives signals for regulating the maturation, proliferation and differentiation of the precursor cells of neutrophilic granulocytes. The signalling complex composed of two GCSFs (GCSF, 19 kDa) and two GCSF receptors (GCSFR, 34 kDa) consisting of an Ig-like domain and a cytokine-receptor homologous (CRH) domain was crystallized. A crystal of the complex was grown in 1.0 M sodium formate and 0.1 M sodium acetate pH 4.6 and belongs to space group P41212 (or its enantiomorph P43212), with unit-cell parameters a = b = 110.1, c = 331.8 Å. Unfortunately, this crystal form did not diffract beyond 5 Å resolution. Since the heterogeneity of GCSF receptor appeared to prevent the growth of good-quality crystals, the GCSF receptor was fractionated by anion-exchange chromatography. Crystals of the GCSF–fractionated GCSF receptor complex were grown as a new crystal form in 0.2 M ammonium phosphate. This new crystal form diffracted to beyond 3.0 Å resolution and belonged to space group P3121 (or its enantiomorph P3221), with unit-cell parameters a = b = 134.8, c = 105.7 Å. PMID:16511159

An unmetasomatized source for the Malaitan alnoeite (Solomon Islands): Petrogenesis involving zone refining, megacryst fractionation, and assimilation of oceanic lithosphere

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

Neal, C.R.; Davidson, J.P.

The Malaitan alnoite contains a rich and varied megacryst suite of unprecedented compositional range. The authors have undertaken trace element and isotope modeling in order to formulate a petrogenetic scheme which links the host alnoeite to its entrained megacrysts. This requires that a proto-alnoeite magma is the product of zone refining initiated by diapiric upwelling (where the initial melt passes through 200 times its volume of mantle). Isotopic evidence indicates the source of the proto-alnoeite contains a time-integrated LREE-depleted signature. Impingement upon the rigid lithosphere halts or dramatically slows the upward progress of the mantle diapir. At this point, themore » magma cools and megacryst fractionation begins with augites crystallizing first, followed by subcalcic diopsides and finally phlogopites. Garnet probably crystallizes over the entire range of clinopyroxene fractionation. Estimated proportions of fractionating phases are 30% augite, 24.5% subcalcic diopside, 27% garnet, 12.9% phlogopite, 5% bronzite, 0.5% ilmenite, and 0.1% zircon. As this proto-alnoeite magma crystallizes, it assimilates a subducted component of seawater-altered basalt which underplates the Ontong Java Plateau. This is witnessed in the isotopic composition of the megacrysts and alnoeite.« less

Abrupt transition from fractional crystallization to magma mixing at Gorely volcano (Kamchatka) after caldera collapse

NASA Astrophysics Data System (ADS)

Gavrilenko, Maxim; Ozerov, Alexey; Kyle, Philip R.; Carr, Michael J.; Nikulin, Alex; Vidito, Christopher; Danyushevsky, Leonid

2016-07-01

A series of large caldera-forming eruptions (361-38 ka) transformed Gorely volcano, southern Kamchatka Peninsula, from a shield-type system dominated by fractional crystallization processes to a composite volcanic center, exhibiting geochemical evidence of magma mixing. Old Gorely, an early shield volcano (700-361 ka), was followed by Young Gorely eruptions. Calc-alkaline high magnesium basalt to rhyolite lavas have been erupted from Gorely volcano since the Pleistocene. Fractional crystallization dominated evolution of the Old Gorely magmas, whereas magma mixing is more prominent in the Young Gorely eruptive products. The role of recharge-evacuation processes in Gorely magma evolution is negligible (a closed magmatic system); however, crustal rock assimilation plays a significant role for the evolved magmas. Most Gorely magmas differentiate in a shallow magmatic system at pressures up to 300 MPa, ˜3 wt% H2O, and oxygen fugacity of ˜QFM + 1.5 log units. Magma temperatures of 1123-1218 °C were measured using aluminum distribution between olivine and spinel in Old and Young Gorely basalts. The crystallization sequence of major minerals for Old Gorely was as follows: olivine and spinel (Ol + Sp) for mafic compositions (more than 5 wt% of MgO); clinopyroxene and plagioclase crystallized at ˜5 wt% of MgO (Ol + Cpx + Plag) and magnetite at ˜3.5 wt% of MgO (Ol + Cpx + Plag + Mt). We show that the shallow magma chamber evolution of Old Gorely occurs under conditions of decompression and degassing. We find that the caldera-forming eruption(s) modified the magma plumbing geometry. This led to a change in the dominant magma evolution process from fractional crystallization to magma mixing. We further suggest that disruption of the magma chamber and accompanying change in differentiation process have the potential to transform a shield volcanic system to that of composite cone on a global scale.

Special Features of the Structure of Single-Crystal Refractory Nickel Alloy Under Directed Crystallization

NASA Astrophysics Data System (ADS)

Bondarenko, Yu. A.; Echin, A. B.; Surova, V. A.; Kolodyazhnyi, M. Yu.

2017-05-01

The effect of the conditions of directed crystallization (the temperature gradient and the crystallization rate) on the dendrite spacing, on the size of the particles of the hardening γ'-phase in the arms and arm spaces of the dendrites, on the volume fraction and size of the pores, on the size of the particles of the eutectic γ/γ'-phase, and on the features of dendritic segregation in a single-crystal castable refractory alloy is studied.

Raw material variability of an active pharmaceutical ingredient and its relevance for processability in secondary continuous pharmaceutical manufacturing.

PubMed

Stauffer, F; Vanhoorne, V; Pilcer, G; Chavez, P-F; Rome, S; Schubert, M A; Aerts, L; De Beer, T

2018-06-01

Active Pharmaceutical Ingredients (API) raw material variability is not always thoroughly considered during pharmaceutical process development, mainly due to low quantities of drug substance available. However, synthesis, crystallization routes and production sites evolve during product development and product life cycle leading to changes in physical material attributes which can potentially affect their processability. Recent literature highlights the need for a global approach to understand the link between material synthesis, material variability, process and product quality. The study described in this article aims at explaining the raw material variability of an API using extensive material characterization on a restricted number of representative batches using multivariate data analysis. It is part of a larger investigation trying to link the API drug substance manufacturing process, the resulting physical API raw material attributes and the drug product continuous manufacturing process. Eight API batches produced using different synthetic routes, crystallization, drying, delumping processes and processing equipment were characterized, extensively. Seventeen properties from seven characterization techniques were retained for further analysis using Principal Component Analysis (PCA). Three principal components (PCs) were sufficient to explain 92.9% of the API raw material variability. The first PC was related to crystal length, agglomerate size and fraction, flowability and electrostatic charging. The second PC was driven by the span of the particle size distribution and the agglomerates strength. The third PC was related to surface energy. Additionally, the PCA allowed to summarize the API batch-to-batch variability in only three PCs which can be used in future drug product development studies to quantitatively evaluate the impact of the API raw material variability upon the drug product process. The approach described in this article could be applied to any other compound which is prone to batch-to-batch variability. Copyright © 2018 Elsevier B.V. All rights reserved.

The Meaning of "Magma"

NASA Astrophysics Data System (ADS)

Bartley, J. M.; Glazner, A. F.; Coleman, D. S.

2016-12-01

Magma is a fundamental constituent of the Earth, and its properties, origin, evolution, and significance bear on issues ranging from volcanic hazards to planetary evolution. Unfortunately, published usages indicate that the term "magma" means distinctly different things to different people and this can lead to miscommunication among Earth scientists and between scientists and the public. Erupting lava clearly is magma; the question is whether partially molten rock imaged at depth and too crystal-rich to flow should also be called magma. At crystal fractions > 50%, flow can only occur via crystal deformation and solution-reprecipitation. As the solid fraction increases to 90% or more, the material becomes a welded crystal framework with melt in dispersed pores and/or along grain boundaries. Seismic images commonly describe such volumes of a few % melt as magma, yet the rheological differences between melt-rich and melt-poor materials make it vital not to confuse a large rock volume that contains a small melt fraction with melt-rich material. To ensure this, we suggest that "magma" be reserved for melt-rich materials that undergo bulk fluid flow on timescales consonant with volcanic eruptions. Other terms should be used for more crystal-rich and largely immobile partially molten rock (e.g., "crystal mush," "rigid sponge"). The distinction is imprecise but useful. For the press, the public, and even earth scientists who do not study magmatic systems, "magma" conjures up flowing lava; reports of a large "magma" body that contains a few percent melt can engender the mistaken perception of a vast amount of eruptible magma. For researchers, physical processes like crystal settling are commonly invoked to account for features in plutonic rocks, but many such processes are only possible in melt-rich materials.

Different magnesium release profiles from W/O/W emulsions based on crystallized oils.

PubMed

Herzi, Sameh; Essafi, Wafa

2018-01-01

Water-in-oil-in-water (W/O/W) double emulsions based on crystallized oils were prepared and the release kinetics of magnesium ions from the internal to the external aqueous phase was investigated at T=4°C, for different crystallized lipophilic matrices. All the emulsions were formulated using the same surface-active species, namely polyglycerol polyricinoleate (oil-soluble) and sodium caseinate (water-soluble). The external aqueous phase was a lactose or glucose solution at approximately the same osmotic pressure as that of the inner droplets, in order to avoid osmotic water transfer phenomena. We investigated two types of crystallized lipophilic systems: one based on blends of cocoa butter and miglyol oil, exploring a solid fat content from 0 to 90% and the other system based on milk fat fractions for which the solid fat content varies between 54 and 86%. For double emulsions based on cocoa butter/miglyol oil, the rate of magnesium release was gradually lowered by increasing the % of fat crystals i.e. cocoa butter, in agreement with a diffusion/permeation mechanism. However for double emulsions based on milk fat fractions, the rate of magnesium release was independent of the % of fat crystals and remains the one at t=0. This difference in diffusion patterns, although the solid content is of the same order, suggests a different distribution of fat crystals within the double globules: a continuous fat network acting as a physical barrier for the diffusion of magnesium for double emulsions based on cocoa butter/miglyol oil and double globule/water interfacial distribution for milk fat fractions based double emulsions, through the formation of a crystalline shell allowing an effective protection of the double globules against diffusion of magnesium to the external aqueous phase. Copyright © 2017 Elsevier Inc. All rights reserved.

Combining Pre- and Post-Nucleation Trajectories for the Synthesis of High FAU-Content Faujasite Nanocrystals from Organic-Free Sols

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

Khaleel, Maryam; Xu, Wenqian; Lesch, David A.

The effects of synthesis conditions on the FAU/EMT content and the size of nanocrystals, formed from inorganic aluminosilicate sols, were investigated. High resolution transmission electron microscopy imaging and comparison of experimental X-ray diffraction patterns with simulations demonstrated that all materials made starting from synthesis mixtures in the composition range (1.8-33) SiO2: 1 Al2O3: (2.7-33) Na2O: (41-1000) H2O contain FAU/EMT intergrowths. Compositions with low water content increase the FAU fraction up to 0.8 but the crystal size exceeds 100 nm. Extension of the higher FAU purity to nanocrystals was achieved only by first mixing the sol at high water content compositionsmore » that favor nanocrystal formation and then - after a certain time - lowering by freeze-drying the water to levels favoring the formation of FAU. Cryogenic transmission electron microscopy and small angle X-ray scattering from representative optically clear and colloidally stable precursor sols (aged and crystallized at ambient temperature) reveal the formation of amorphous aggregates before the detection of crystals, in agreement with earlier findings and an existing model for the aggregative growth of the zeolite MFI. The presence of these amorphous aggregates coincides with the aforementioned state of sol that preserves the original trajectory towards nano-crystals after the pronounced reduction of water content by freeze-drying. If water reduction by freeze-drying is applied earlier (before the detection of amorphous aggregates), the sol follows the low water content trajectory towards larger crystals. Despite this memory effect, the sol at this stage is still agnostic towards FAU or EMT formation, the relative content of which is dominantly determined by the final water content. These findings demonstrate that it is possible to combine the effects of pre-and post-nucleation sol composition to steer crystal size and crystal structure, respectively. They confirm precursor nanoparticle evolution, while they emphasize the importance of solution phase composition at both pre- and post-nucleation stages of aggregative crystal growth.« less

Understanding Melt-Memory of Commercial Polyolefins

NASA Astrophysics Data System (ADS)

Alamo, Rufina

Self-nucleation (SN) or controlling self-generated seeds in a polymer melt is an avenue to increase the rate of solidification of semicrystalline polymers of commercial relevance. Self-nuclei are remains in the melt of the segmental self-assembly to form polymer crystallites providing a path to enhance primary crystal nucleation. SN has been extensively studied in homopolymers such as iPP. Recently, a strong memory effect of crystallization has been observed in melts of random ethylene copolymers well above the equilibrium melting temperature. The melt memory is associated with clusters or seeds that remain in the melt from the copolymer's sequence length partitioning. Cooling from progressively lower self-seeded melt temperatures, ethylene copolymers with a broad inter-chain comonomer composition (1 - 15 mol%) display first the expected accelerated crystallization, followed by a decrease in the rate in a range of melt temperatures where narrow copolymers show a continuous acceleration of the rate. This unusual inversion of the crystallization rate was postulated to arise from the onset of liquid-liquid phase separation (LLPS) between comonomer-rich and comonomer-poor components of the broad copolymer. The UCST type phase diagram of these commercial copolymers has been documented via SANS using a blend of components, some deuterated, to reproduce the broad distribution. Furthermore, the components that contribute to LLPS have been identified by the crystallization behavior of molar mass fractions. The influence of long chain branching on the topology of copolymer melts has been analyzed using model 3-arm stars hydrogenated polybutadienes. The effect of melt viscosity on strength of melt memory is also evident when SN data of random ethylene copolymers are compared with those of propylene-ethylene copolymers. The strong dependence of melt viscosity on melt memory, and a critical threshold crystallinity level to observe the effect of melt memory on crystallization rate, support the kinetic nature of the SN phenomenon. Support from NSF, DMR-1105129 and DMR-1607786 is gratefully acknowledged.

High-temperature electroacoustic characterization of Y-cut and singly-rotated Ca3TaGa3Si2O14 resonators.

PubMed

Johnson, Ward L; Schulz, Michal; Fritze, Holger

2014-08-01

Synthetic piezoelectric crystals in the P321 crystal class have been a focus of substantial research that is largely driven by applications in high-temperature resonant BAW and SAW sensing. Fully ordered crystals in this class, such as Ca3TaGa3Si2O14 (CTGS), have been suggested as offering the potential of electroacoustic performance that is superior to more extensively studied langasite (LGS) and langatate (LGT), which are partially disordered. In this study, the resonant frequencies, acoustic damping, and electrical conductivity of CTGS bulk acoustic resonators with Y-cut and (YXl)-30° crystal orientations and fundamental frequencies near 5 MHz are investigated at temperatures between ambient and 1100°C. (YXl)-30° resonators are found to have turnover temperatures near 200°C for the third and fifth overtones, in contrast to a monotonic decrease in resonant frequencies of Y-cut crystals with increasing temperature. The maximum temperature derivative of fractional changes in fifth-overtone frequency of (YXl)-30° CTGS is 40 × 10-6K-1 (near 1100°C), and this value is not greatly different from the temperature derivative of Y-cut CTGS frequencies over a broader range of temperatures. At ambient temperatures, the acoustic loss Q-1 of CTGS with both crystal orientations is found to be greater than the lowest values previously reported for LGS and LGT. The electrical conductivity of the CTGS specimens between 500°C and 1100°C is substantially lower than that previously reported for LGS. Corresponding to this lower conductivity, the piezoelectric/conductive contribution to Q-1 at elevated temperatures is reduced. Additional anelastic relaxation peaks observed between 100°C and 700°C are similar to those previously reported for LGS and LGT.

Structure of the mixed-metal carbonate KAgCO₃ revisited: order-disorder (OD) polytypism and allotwinning.

PubMed

Hans, Philipp; Stöger, Berthold; Weil, Matthias; Zobetz, Erich

2015-04-01

Crystals of KAgCO3 belong to an order-disorder (OD) family of structures composed of layers of two kinds. There are two polytypes with a maximum degree of order [MDO1: Pccb; MDO2: Ibca, doubled a-axis compared with MDO1], which are both realised to a different extent in two crystals under investigation [volume fraction MDO1:MDO2 in crystal (I): 0.0216:0.9784 (3) and in crystal (II): 0.9657:0.0343 (3)]. Sharp diffraction spots and the absence of diffuse scattering indicate highly ordered macroscopic domains. The structure of KAgCO3 was refined concurrently against all reflections using an allotwin model (addition of the intensities of both domains). It is shown that a disorder model refined against reflections of only one domain can lead to a significant overestimation of the volume fraction of this domain.

Planetoid core crystallisation and fractionation - Evidence from the Agpalilik mass of the Cape York iron meteorite shower

NASA Astrophysics Data System (ADS)

Esbensen, K. H.; Buchwald, V. F.

1982-09-01

Metallographic and chemical study of the Agpalik mass of the Cape York iron meteorite shower reveals evidence of the mode of crystallization and fractionation of key elements consistent with a dendritic solidification of at least part of the once fully molten parent body's metallic core. Chemical gradients of Ir and Au are assessed across an 85 cm section that is inferred to be perpendicular to the parent body's gravitational field, and are interpreted as representing a dendritic growth mode. The characteristic elongated and orientated sulfide nodules found in Agpalik signify trapped liquid of the latest stages of crystallization. Detailed mineralogical and chemical characterization of the Agpalik liquid-solid transformation products allow modelling of the entire crystallization history commencing with dendritic metal precipitation through an ultimate troilite-taenite-Cu eutectic, representing a crystallization range spanning approximately 1350-700 C.

Evidence for high-temperature fractionation of lithium isotopes during differentiation of the Moon

NASA Astrophysics Data System (ADS)

Day, James M. D.; Qiu, Lin; Ash, Richard D.; McDonough, William F.; Teng, Fang-Zhen; Rudnick, Roberta L.; Taylor, Lawrence A.

2016-06-01

Lithium isotope and abundance data are reported for Apollo 15 and 17 mare basalts and the LaPaz low-Ti mare basalt meteorites, along with lithium isotope data for carbonaceous, ordinary, and enstatite chondrites, and chondrules from the Allende CV3 meteorite. Apollo 15 low-Ti mare basalts have lower Li contents and lower δ7Li (3.8 ± 1.2‰; all uncertainties are 2 standard deviations) than Apollo 17 high-Ti mare basalts (δ7Li = 5.2 ± 1.2‰), with evolved LaPaz mare basalts having high Li contents, but similar low δ7Li (3.7 ± 0.5‰) to Apollo 15 mare basalts. In low-Ti mare basalt 15555, the highest concentrations of Li occur in late-stage tridymite (>20 ppm) and plagioclase (11 ± 3 ppm), with olivine (6.1 ± 3.8 ppm), pyroxene (4.2 ± 1.6 ppm), and ilmenite (0.8 ± 0.7 ppm) having lower Li concentrations. Values of δ7Li in low- and high-Ti mare basalt sources broadly correlate negatively with 18O/16O and positively with 56Fe/54Fe (low-Ti: δ7Li ≤4‰; δ56Fe ≤0.04‰; δ18O ≥5.7‰; high-Ti: δ7Li >6‰ δ56Fe >0.18‰ δ18O <5.4‰). Lithium does not appear to have acted as a volatile element during planetary formation, with subequal Li contents in mare basalts compared with terrestrial, martian, or vestan basaltic rocks. Observed Li isotopic fractionations in mare basalts can potentially be explained through large-degree, high-temperature igneous differentiation of their source regions. Progressive magma ocean crystallization led to enrichment in Li and δ7Li in late-stage liquids, probably as a consequence of preferential retention of 7Li and Li in the melt relative to crystallizing solids. Lithium isotopic fractionation has not been observed during extensive differentiation in terrestrial magmatic systems and may only be recognizable during extensive planetary magmatic differentiation under volatile-poor conditions, as expected for the lunar magma ocean. Our new analyses of chondrites show that they have δ7Li ranging between -2.5‰ and 4‰. The higher δ7Li in planetary basalts than in the compilation of chondrites (2.1 ± 1.3‰) demonstrates that differentiated planetary basalts are, on average, isotopically heavier than most chondrites.

Petrogenesis of Western Cascades Silicic Volcanics Near Sweet Home, Oregon

NASA Astrophysics Data System (ADS)

Cook, G. W.; White, C. M.

2002-12-01

Silicic lavas in the Menagerie Wilderness east of Sweet Home, Oregon are Oligocene to Miocene in age and range in composition from dacite (low K) to trachydacite (high K) and rhyolite (medium K). Three distinct silicic centers have been distinguished through a combination of field observation, chemistry and petrography. Phenocryst assemblages in rocks of the centers are plagioclase-hornblende-magnetite (Rooster Rock rhyolite), plagioclase-quartz-magnetite (Soda Fork rhyolite) and quartz-plagioclase-biotite-hornblende-magnetite (Moose Mt. rhyolite). The silicic volcanics in the study area are similar in terms of mineral content and overall chemical composition. Despite this, chemical evidence suggests that the three centers are petrologically unrelated. REE variations and least squares modeling of major element compositions are consistent with fractionation of plagioclase and hornblende. The rhyolites have moderate Eu anomalies and have flat MREE and HREE signatures. Least squares models and bivariate plots of major and trace elements also suggest fractionation of the aforementioned phases for both the andesite to dacite, and dacite to rhyolite steps. Comparisons with similar silicic centers show the Menagerie rocks share affinities with High Cascades rocks thought to have been derived through fractional crystallization (Crater Lake and South Sister). Plots of ratios of incompatible trace elements were utilized to determine if assimilation played some role alongside fractional crystallization in differentiation. Plots of Ba/La vs. Ba, Rb/Zr vs. Rb and Rb/Th vs. Rb show systematic positive increases in the ratios between a plausible parent magma (icelandite) and the rhyolites. These increases are not easily explained by fractional crystallization but can be modeled by assimilation of silicic crust. Overall, it seems likely that the three centers evolved independently through similar petrogenetic processes from an andesitic parent. The most plausible petrogenetic scenario involves some combination of fractional crystallization and assimilation of partial melts of silicic crust.

Crystal structure and phase transition of thermoelectric SnSe.

PubMed

Sist, Mattia; Zhang, Jiawei; Brummerstedt Iversen, Bo

2016-06-01

Tin selenide-based functional materials are extensively studied in the field of optoelectronic, photovoltaic and thermoelectric devices. Specifically, SnSe has been reported to have an ultrahigh thermoelectric figure of merit of 2.6 ± 0.3 in the high-temperature phase. Here we report the evolution of lattice constants, fractional coordinates, site occupancy factors and atomic displacement factors with temperature by means of high-resolution synchrotron powder X-ray diffraction measured from 100 to 855 K. The structure is shown to be cation defective with a Sn content of 0.982 (4). The anisotropy of the thermal parameters of Sn becomes more pronounced approaching the high-temperature phase transition (∼ 810 K). Anharmonic Gram-Charlier parameters have been refined, but data from single-crystal diffraction appear to be needed to firmly quantify anharmonic features. Based on modelling of the atomic displacement parameters the Debye temperature is found to be 175 (4) K. Conflicting reports concerning the different coordinate system settings in the low-temperature and high-temperature phases are discussed. It is also shown that the high-temperature Cmcm phase is not pseudo-tetragonal as commonly assumed.

Evolution of the Craters of the Moon Lavas from primitive Snake River Plain basalts: inferences from plagioclase-melt thermobarometers and whole rock compositions

NASA Astrophysics Data System (ADS)

Vaid, N.; Putirka, K.; Kuntz, M.

2005-12-01

The volcanic rocks of the Craters of the Mon Lava field provide an ideal laboratory for testing models of magma transport and evolution. Their compositions, relative ages and volumes are well known, as are the fractionation processes leading to their evolution (Leeman, 1976). The COM is somewhat distinctive in the Snake River Plain (SRP) region, due to its evolved character, and an apparent compositional segregation from associated SRP basalts. Some have suggested that the high Fe liquids of the COM demand an origin separate from that of SRP basalts, possibly involving an Fe-enriched mantle, while others have suggested that the COM lavas may be derived by fractionation at moderate depths (30 km). In either case, there are important implications in regard to mantle composition and the nature and distribution of thermal energy. We use plagioclase-melt pairs and an analysis of whole rock compositions in attempt to test models of COM magmatic evolution. Plagioclase-melt thermobarometers provide rough estimates of crystallization depths, and show that COM and SRP lavas partially crystallized at similar depths of 14 +/- 6 km. However, plagioclase crystallization temperatures for SRP basalts (1400 +/- 25 K; Kings Bowl, Cerro Grande, North and South Robbers) exceed temperatures for COM lavas (1358 +/- 45 K) by 40 K. Our data also show that fractional crystallization (ol + plag) can explain the evolution of surrounding SRP basalt flows, and that the most evolved SRP basalts approach primitive COM lava compositions. The most primitive of COM magmas appear to be characterized by the appearance of apatite + magnetite as fractionating phases. Our results thus confirm the geochemical model of Leeman (1976) and the physical model of Kuntz (1992), with the added insight that SRP basalts are parental to the more evolved COM lavas, through low-pressure fractional crystallization in the upper crust. The principal differences between SRP and COM magmas appear to relate more to the presence or absence of density contrasts in the crust than differences in composition or temperature of mantle source materials. SRP basalts lie near the axis of the SRP where the granitic upper crust may have been obliterated by earlier volcanic episodes. In contrast, COM lavas, whose vents lie off axis, appear to have been trapped within the upper crust for longer periods, sufficient for further differentiation. Finally, SRP rhyolite compositions lie on the same fractionation trend as COM and SRP lavas, at very low values of MgO. We propose that highly evolved lavas throughout the SRP may form by fractional crystallization mechanisms alone, rather than through the partial melting and remobilization of preexisting felsic crustal materials.

Light scattering by hexagonal ice crystals with distributed inclusions

NASA Astrophysics Data System (ADS)

Panetta, R. Lee; Zhang, Jia-Ning; Bi, Lei; Yang, Ping; Tang, Guanlin

2016-07-01

Inclusions of air bubbles or soot particles have significant effects on the single-scattering properties of ice crystals, effects that in turn have significant impacts on the radiation budget of an atmosphere containing the crystals. This study investigates some of the single-scattering effects in the case of hexagonal ice crystals, including effects on the backscattering depolarization ratio, a quantity of practical importance in the interpretation of lidar observations. One distinguishing feature of the study is an investigation of scattering properties at a visible wavelength for a crystal with size parameter (x) above 100, a size regime where one expects some agreement between exact methods and geometrical optics methods. This expectation is generally borne out in a test comparison of how the sensitivity of scattering properties to the distribution of a given volume fraction of included air is represented using (i) an approximate Monte Carlo Ray Tracing (MCRT) method and (ii) a numerically exact pseudo-spectral time-domain (PSTD) method. Another distinguishing feature of the study is a close examination, using the numerically exact Invariant-Imbedding T-Matrix (II-TM) method, of how some optical properties of importance to satellite remote sensing vary as the volume fraction of inclusions and size of crystal are varied. Although such an investigation of properties in the x>100 regime faces serious computational burdens that force a large number of idealizations and simplifications in the study, the results nevertheless provide an intriguing glimpse of what is evidently a quite complex sensitivity of optical scattering properties to inclusions of air or soot as volume fraction and size parameter are varied.

Raman tensor elements for tetragonal BaTiO3 and their use for in-plane domain texture assessments

NASA Astrophysics Data System (ADS)

Deluca, Marco; Higashino, Masayuki; Pezzotti, Giuseppe

2007-08-01

A quantitative assessment of c-axis oriented domains in a textured BaTiO3 (BT) single crystal has been carried out by polarized Raman microprobe spectroscopy. The relative intensity modulation of the Raman phonon modes has been theoretically modeled as a function of crystal rotation and linked to the volume fraction of c-axis oriented domains. Raman tensor elements have also been experimentally determined for the Ag and B1 vibrational modes. As an application, the internal in-plane texture and the volume fraction of c-oriented domains in the BT single crystal have been nondestructively visualized by monitoring the relative intensity of Ag and B1 Raman modes.

Antioxidant and anticholinesterase potential of diterpenoid alkaloids from Aconitum heterophyllum.

PubMed

Ahmad, Hanif; Ahmad, Shujaat; Shah, Syed Adnan Ali; Latif, Abdul; Ali, Mumtaz; Khan, Farman Ali; Tahir, Muhammad Nawaz; Shaheen, Farzana; Wadood, Abdul; Ahmad, Manzoor

2017-07-01

Extensive chromatographic separations performed on the basic (pH=8-10) chloroform soluble fraction of Aconitum heterophyllum resulted in the isolation of three new diterpenoid alkaloids, 6β-Methoxy, 9β-dihydroxylheteratisine (1), 1α,11,13β-trihydroxylhetisine (2), 6,15β-dihydroxylhetisine (3), and the known compounds iso-atisine (4), heteratisine (5), hetisinone (6), 19-epi-isoatisine (7), and atidine (8). Structures of the isolated compounds were established by means of mass and NMR spectroscopy as well as single crystal X-ray crystallography. Compounds 1-8 were screened for their antioxidant and enzyme inhibition activities followed by in silico studies to find out the possible inhibitory mechanism of the tested compounds. This work is the first report demonstrating significant antioxidant and anticholinesterase potentials of diterpenoid alkaloids isolated from a natural source. Copyright © 2017 Elsevier Ltd. All rights reserved.

Pyroclastics Northeast of Gassendi Crater: Discovery/Characteristics/Implications

NASA Technical Reports Server (NTRS)

Giguere, T. A.; Hawke, B. R.; Trang, D.; Gaddis, L. R.; Lawrence, S. J.; Stopar, J. D.; Gustafson, J. O.; Boyce, J. M.; Gillis-Davis, J. J.

2017-01-01

In our ongoing effort to better understand lunar volcanism on the Moon, we are investigating pyroclastic deposits in the Gassendi region. Interest in pyroclastics has remained high due to the availability of high-resolution data (LRO, Kaguya), which is used to build on previous remote sensing studies [e.g., 1, 2, 3] and also extensive studies of lunar pyroclastic glasses [4, 5]. Analyses conducted in the laboratory of pyroclastic spheres from several deposits show that this volcanic material had a greater depth of origin and lesser fractional crystallization than mare basalts [e.g., 4, 6]. Data indicates that pyroclastic glasses are the best examples of primitive materials on the Moon, and they are important for both characterizing the lunar interior and as a starting place for under-standing the origin and evolution of lunar basaltic magmatism [2].

Minor and trace element geochemistry of volcanic rocks dredged from the Galapagos spreading center: role of crystal fractionation and mantle heterogeneity.

USGS Publications Warehouse

Clague, D.A.; Frey, F.A.; Thompson, G.; Rindge, S.

1981-01-01

A wide range of rock types (abyssal tholeiite, Fe-Ti-rich basalt, andesite, and rhyodacite) were dredged from near 95oW and 85oW on the Galapagos spreading center. Computer modeling of major element compositions has shown that these rocks could be derived from common parental magmas by successive degrees of fractional crystallization. However, the P2O5/K2O ratio implies distinct mantle source compositions for the two areas. These source regions also have different rare earth element (REE) abundance patterns. The sequence of fractionated lavas differs for the two areas and indicates earlier fractionation of apatite and titanomagnetite in the lavas from 95oW. The mantle source regions for these two areas are interpreted to be depleted in incompatible (and volatile?) elements, although the source region beneath 95oW is less severely depleted in La and K. -Authors

Characterization of lycopene hydrocolloidal structure induced by tomato processing.

PubMed

Jazaeri, Sahar; Mohammadi, Abdorreza; Kermani, Amir Mehrabi Panah; Paliyath, Gopinadhan; Kakuda, Yukio

2018-04-15

Tomato juice and paste are special type of dispersions, composed of suspended particles (pulp) dispersed in a colloidal liquid medium (serum). The bright red appearance of soluble solid separated by high speed centrifugation denoted the presence of lycopene in this fraction. Since lycopene is a hydrophobic compound it is not expected to appear in the water soluble fraction. HPLC analysis indicated presence of substantial amount of lycopene in soluble fraction which was confirmed by the appearance of lycopene crystals when observed under Transmission Electron Microscope (TEM). Considerable amount of pectin in the soluble fraction led to hypothesis that pectin facilitated the formation of hydrocolloidal system of suspended lycopene during processing. Enzyme treatment confirmed this hypothesis when pectinase effectively disrupted colloidal system and precipitated lycopene. Necessity of the divalent ions to retain the suspension signified the electrostatic interactions in the matrix surrounding lycopene crystals. Copyright © 2017 Elsevier Ltd. All rights reserved.

Characterization of polypropylene–polyethylene blends by temperature rising elution and crystallization analysis fractionation

PubMed Central

del Hierro, Pilar

2010-01-01

The introduction of single-site catalysts in the polyolefins industry opens new routes to design resins with improved performance through multicatalyst-multireactor processes. Physical combination of various polyolefin types in a secondary extrusion process is also a common practice to achieve new products with improved properties. The new resins have complex structures, especially in terms of composition distribution, and their characterization is not always an easy task. Techniques like temperature rising elution fractionation (TREF) or crystallization analysis fractionation (CRYSTAF) are currently used to characterize the composition distribution of these resins. It has been shown that certain combinations of polyolefins may result in equivocal results if only TREF or CRYSTAF is used separately for their characterization. PMID:20730530

Chondritic late accretion to Mars and the nature of shergottite reservoirs

NASA Astrophysics Data System (ADS)

Tait, Kim T.; Day, James M. D.

2018-07-01

Mars is considered to have formed as a planetary embryo that experienced extensive differentiation early in its history. Shergottite meteorites preserve evidence for this history, and for late accretion events that affected their mantle sources within Mars. Here we report the first coupled 187Re-187Os, 87Sr/86Sr, highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, Re) and major element abundance dataset for martian shergottites that span a range of MgO contents, from 6.4 to 30.3 wt.%. The shergottites range from picro-basalt to basaltic-andesite compositions, have enriched to depleted incompatible trace-element compositions, and define fractional crystallization trends, enabling the determination of HSE compatibility for martian magmatism in the order: Os > Ir ≥ Ru ≫ Pt ≥ Pd ≥ Re. This order of compatibility is like that defined previously for Earth and the Moon, but the fractionation of strongly compatible Os, Ir and Ru appears to take place at higher MgO contents in martian magmas, due to early onset of sulfide fractionation. In general, enriched shergottites have lower MgO contents than intermediate or depleted shergottites and have fractionated HSE patterns (Re + Pd + Pt > Ru + Ir + Os) and more radiogenic measured 87Sr/86Sr (0.7127-0.7235) and 187Os/188Os (0.140-0.247) than intermediate or depleted shergottite meteorites (87Sr/86Sr = 0.7010-0.7132; 187Os/188Os = 0.127-0.141). Osmium isotope compositions, corrected for crystallization age, define compositions that are implausibly unradiogenic in some enriched shergottites, implying recent mobilization of Re in some samples. Filtering for the effects of alteration and high Re/Os through crystal-liquid fractionation leads to a positive correlation between age-corrected Sr and Os isotope compositions. Mixing between hypothetical martian crustal and mantle reservoirs are unable to generate the observed Sr-Os isotope compositions of shergottites, which require either distinct and discrete long-term incompatible-element depleted and enriched mantle sources, or originate from hybridized melting of deep melts with metasomatized martian lithosphere. Using MgO-regression methods, we obtain a modified estimate of the bulk silicate Mars HSE composition of (in ng g-1) 0.4 [Re], 7.4 [Pd], 9.6 [Pt], 6.2 [Ru], 3.7 [Ir], 4 [Os], and a long-term chondritic 187Os/188Os ratio (∼0.1312). This result does not permit existing models invoking high-pressure and temperature partitioning of the HSE. Instead, our estimate implies 0.6-0.7% by mass of late accretion of broadly chondritic material to Mars. Our results indicate that Mars could have accreted earlier than Earth, but that disproportional accretion of large bodies and a relative constant flux of accretion of available materials in the first 50-100 Ma of Solar System led to the broad similarity in HSE abundances between Earth and Mars.

Resonant coherent excitation of relativistic Ar 17+ ions channeled in a Si crystal

NASA Astrophysics Data System (ADS)

Azuma, T.; Ito, T.; Yamazaki, Y.; Komaki, K.; Sano, M.; Torikoshi, M.; Kitagawa, A.; Takada, E.; Murakami, T.

1998-02-01

We observed resonant coherent excitation (RCE) of 1s electron to n=2 states in Ar 17+ through measurements of the survived fraction of 390 MeV/u hydrogen-like Ar 17+ channeled in a Si crystal. We adopted a totally depleted Si surface barrier detector as a target crystal as well as a probe of the energy deposition. The charge state of emerged ions was measured by a combination of a charge separation magnet and a 2D-position sensitive detector. We observed the RCE for planar channeled ions by tilting the target Si crystal from the direction of [1 1 0] axis in the (2 2¯ 0) , (0 0 4) , and (1 1¯ 1) planes. Prominent resonances at tilt angles under the resonance condition were observed. Moreover, each resonance profile is split into several lines due to the l· s interaction and the Stark effect originating in the static crystal field. The energy deposition in the crystal gives the information of the amplitude of the ion trajectory. The resonance peak position, intensity and width in the survived fraction of Ar 17+ reflect the position dependent strength of the crystal field, the RCE and the electron loss probabilities. They are in good accord with our calculation of the transition energy and probability.

Cadmium cycling in the water column of the Kuroshio-Oyashio Extension region: Insights from dissolved and particulate isotopic composition

NASA Astrophysics Data System (ADS)

Yang, Shun-Chung; Zhang, Jing; Sohrin, Yoshiki; Ho, Tung-Yuan

2018-07-01

We measured dissolved and particulate Cd isotopic composition in the water column of a meridional transect across the Kuroshio-Oyashio Extension region in a Japanese GEOTRACES cruise to investigate the relative influence of physical and biogeochemical processes on Cd cycling in the Northwestern Pacific Ocean. Located at 30-50°N along 165°E, the transect across the extension region possesses dramatic hydrographic contrast. Cold surface water and a relatively narrow and shallow thermocline characterizes the Oyashio Extension region in contrast to a relatively warm and highly stratified surface water and thermocline in the Kuroshio Extension region. The contrasting hydrographic distinction at the study site provides us with an ideal platform to investigate the spatial variations of Cd isotope fractionation systems in the ocean. Particulate samples demonstrated biologically preferential uptake of light Cd isotopes, and the fractionation effect varied dramatically in the surface water of the two regions, with relatively large fractionation factors in the Oyashio region. Based on the relationship of dissolved Cd concentrations and isotopic composition, we found that a closed system fractionation model can reasonably explain the relationship in the Kuroshio region. However, using dissolved Cd isotopic data, either a closed system or steady-state open system fractionation model may explain the relationship in the surface water of the Oyashio region. Particulate δ114/110Cd data further supports that the surface water of the Oyashio region matches a steady-state open system model more closely. Contrary to the surface water, the distribution of potential density exhibits comparable patterns with Cd elemental and isotopic composition in the thermocline and deep water in the two extension regions, showing that physical processes are the dominant forcing controlling Cd cycling in the deep waters. The results demonstrate that Cd isotope fractionation can match either a closed or open system Rayleigh fractionation model, depending on the relative contribution of physical and biogeochemical processes on its cycling.

Residual glasses and melt inclusions in basalts from DSDP Legs 45 and 46 - Evidence for magma mixing. [Deep Sea Drilling Project

NASA Technical Reports Server (NTRS)

Dungan, M. A.; Rhodes, J. M.

1978-01-01

Microprobe analyses of natural glasses in basalts recovered by Legs 45 and 46 of the Deep Sea Drilling Project are reported and interpreted in the context of other geochemical, petrographic and experimental data on the same rocks (Rhodes et al., 1978). Residual glass compositions in the moderately evolved aphyritic and abundantly phyric basalts within each site indicate that none of the units is related to any other or to a common parent by simple fractional crystallization. The compositional trends, extensive disequilibrium textures in the plagioclase phenocrysts and the presence in evolved lavas of refractory plagioclase and olivine phenocrysts bearing primitive melt inclusions provide evidence that magma mixing had a major role in the genesis of the Leg 45 and 46 basalts. The magma parental to these basalts was most likely characterized by high Mg/(Mg + Fe/+2/), CaO/Al2O3, CaO/Na2O and low lithophile concentrations. A mixing model involving incremental enrichment of magmaphile elements by repeated episodes of mixing of relatively primitive and moderately evolved magmas, followed by a small amount of fractionation is consistent with the characteristics of the basalts studied.

Inhibition of ice crystal growth in ice cream mix by gelatin hydrolysate.

PubMed

Damodaran, Srinivasan

2007-12-26

The inhibition of ice crystal growth in ice cream mix by gelatin hydrolysate produced by papain action was studied. The ice crystal growth was monitored by thermal cycling between -14 and -12 degrees C at a rate of one cycle per 3 min. It is shown that the hydrolysate fraction containing peptides in the molecular weight range of about 2000-5000 Da exhibited the highest inhibitory activity on ice crystal growth in ice cream mix, whereas fractions containing peptides greater than 7000 Da did not inhibit ice crystal growth. The size distribution of gelatin peptides formed in the hydrolysate was influenced by the pH of hydrolysis. The optimum hydrolysis conditions for producing peptides with maximum ice crystal growth inhibitory activity was pH 7 at 37 degrees C for 10 min at a papain to gelatin ratio of 1:100. However, this may depend on the type and source of gelatin. The possible mechanism of ice crystal growth inhibition by peptides from gelatin is discussed. Molecular modeling of model gelatin peptides revealed that they form an oxygen triad plane at the C-terminus with oxygen-oxygen distances similar to those found in ice nuclei. Binding of this oxygen triad plane to the prism face of ice nuclei via hydrogen bonding appears to be the mechanism by which gelatin hydrolysate might be inhibiting ice crystal growth in ice cream mix.

The evolution of the magmatic arc of Southern Peru (200-60 Ma), Arequipa area: insight from geochemical modeling

NASA Astrophysics Data System (ADS)

Demouy, S.; Benoit, M.; De Saint Blanquat, M.; Brunet, P.

2012-12-01

Cordilleran-type batholiths are built by prolonged arc activity along continental margins and may provide detailed magmatic records of the subduction system evolution. The magmas produced in subduction context involve both mantellic and crustal end members and are subject to various petrological processes. The MASH zones (Hildreth and Moorbath, 1988), at the basis of the continental crust, are the best places for the genesis of such hybrid magmas. The various geochemical signatures observed in the plutonic rocks, may also be attributed to source heterogeneities or generated by subsequent petrological processes. This study has focused in the Arequipa section of the Coastal Batholith of Southern Peru (200-60 Ma), in an area extending over 80x40 km. Major and trace elements as well as Sr and Nd isotopic analyses were performed in a set of 100 samples ranging from gabbro to granite. The obtained data highlight the wide heterogeneity of the geochemical signatures that is not related to the classification of the rocks. In first step, Rb/Sr systematic was used to isolate a set of samples plotting along a Paleocene isochron and defining a cogenetic suite. This suite appears to have evolved by simple fractional crystallization. By using reverse modeling, the parameters controlling the fractional crystallization process were defined, as partition coefficients, initial concentrations and amount of fractional crystallization. The other magmatic suites display a wide range of isotopic and geochemical signatures. To explain this heterogeneity, a model involving competition between fractional crystallization and magma mixing into MASH zones was proposed. A large range of hybrid magma types is potentially generated during the maturation of the system, but this range tends to disappear as fractionation and mixing occurs. Finally the model predicts the genesis of a homogeneous reservoir created at depth, from which magmas may evolve only by fractional crystallization. Therefore stabilization of this reservoir is directly related to the thermal conditions present at the basis of the continental crust, and allows the production of large volumes at the batholiths level, known as flare-up events. These results are critical in order to estimate the amount of crustal growth and thickening in the Arequipa area, as they provide the basis for the estimation of the mantle versus crustal contribution during the magma genesis.

Copper isotope behavior during extreme magma differentiation and degassing: a case study on Laacher See phonolite tephra (East Eifel, Germany)

NASA Astrophysics Data System (ADS)

Huang, Jian; Liu, Sheng-Ao; Wörner, Gerhard; Yu, Huimin; Xiao, Yilin

2016-09-01

Copper (Cu) isotopic analyses were performed on a set of samples from the Laacher See tephra (LST) (Eifel, Germany) to investigate whether Cu isotopes are fractionated during extreme magma differentiation and degassing. The LST represents a continuous fractional crystallization series from parental basanite through mafic to highly differentiated phonolites. Samples analyzed here include phonolites of variable degrees of differentiation, phonolite-basanite hybrid rocks formed by mixing basanite and phonolite magmas, and basanite-derived mega-crystals (i.e., clinopyroxene, amphibole, phlogopite). In addition, we analyzed a series of mafic parental lavas from surrounding volcanic centers to constrain the Cu isotopic features of the Eifel mantle. Mafic phonolites show strong depletion in Cu compared to their parental basanites from ~50 to ~3 ppm, indicating sulfide fractionation during the basanite-to-phonolite differentiation. Mass balance calculations, based on the most Cu-rich hybrid rock (δ65Cu = -0.21 ‰, [Cu] = 46.2 ppm), show that the parental basanite magmas have δ65Cu of ca. -0.21 ‰, lighter than those of the mafic phonolites (~0.11 ‰). This suggests that sulfide fractionation preferentially removes the lighter Cu isotope (63Cu) in S-saturated magmas. By contrast, all phonolites have a limited range of Cu contents (1.1 to 4.0 ppm) with no systematic variations with S, suggesting that Cu is not controlled by sulfide fractionation during the evolution of mafic to highly differentiated phonolites. The identical δ65Cu values (0.11 ± 0.03 ‰, 2SD, n = 10) of the phonolites, irrespective of highly diverse composition and extents of differentiation, indicate that fractional crystallization of silicates (e.g., plagioclase, sanidine, amphibole, pyroxene, olivine), Fe-Ti-oxides and phosphate (e.g., apatite) generates insignificant Cu isotope fractionation. The lack of correlations between δ65Cu and volatile contents (e.g., S, Cl) in the LST sequence implies that volcanic degassing causes no detectable Cu isotope fractionation of igneous rocks. Eifel basalts and mega-crystals have variable δ65Cu (-0.18 to 0.21 ‰) that are uncorrelated to MgO and Cu, suggesting that such variations were not caused by differentiation but reflect the Cu isotopic heterogeneity of the Eifel mantle source due to metasomatism by fluids derived from hydrothermally altered oceanic lithosphere.

Photoacoustic and luminescence spectroscopy of benzil crystals

NASA Astrophysics Data System (ADS)

Bonno, B.; Laporte, J. L.; Rousset, Y.

1991-06-01

In the present work, both photoacoustic and luminescence techniques were employed to study molecular crystals. This paper presents an extension of the standard Rosencwaig-Gersho photoacoustic model to molecular crystals, which includes finite-deexcitation-time effects and excited-state populations. In the temperature range 100-300 K, the phosphorescence quantum yield and thermal diffusivity of benzil crystals were determined.

Differentiation of magma oceans and the thickness of the depleted layer on Venus

NASA Technical Reports Server (NTRS)

Solomatov, V. S.; Stevenson, D. J.

1993-01-01

Various arguments suggest that Venus probably has no asthenosphere, and it is likely that beneath the crust there is a highly depleted and highly viscous mantle layer which was probably formed in the early history of the planet when it was partially or completely molten. Models of crystallization of magma oceans suggest that just after crystallization of a hypothetical magma ocean, the internal structure of Venus consists of a crust up to about 70 km thickness, a depleted layer up to about 500 km, and an enriched lower layer which probably consists of an undepleted 'lower mantle' and heavy enriched accumulates near the core-mantle boundary. Partial or even complete melting of Venus due to large impacts during the formation period eventually results in differentiation. However, the final result of such a differentiation can vary from a completely differentiated mantle to an almost completely preserved homogeneous mantle depending on competition between convection and differentiation: between low viscosity ('liquid') convection and crystal settling at small crystal fractions, or between high viscosity ('solid') convection and percolation at large crystal fractions.

Investigation of crystalline morphology in poly (ether ether ketone) using dielectric relaxation spectroscopy

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

Kalika, D.S.; Krishnaswamy, R.K.

1993-12-31

The relaxation behavior of poly (ether ether ketone) [PEEK] has been investigated using dielectric relaxation spectroscopy; the glass-rubber ({alpha}) relaxation and a sub-glass ({beta}) relaxation were examined for the amorphous material and both cold-crystallized and melt-crystallized specimens. Analysis of the data using the Cole-Cole modification of the Debye equation allowed determination of the dielectric relaxation strength and relaxation broadening parameter for both transitions as a function of material crystallization history. The crystallized specimens displayed a positive offset in isochronal loss temperature for both the {alpha} and {beta} relaxations, with the {alpha} relaxation broadened significantly. The measured dipolar response was interpretedmore » using a three-phase morphological model encompassing a crystalline phase, a mobile amorphous phase, and a rigid amorphous phase. Determination of phase fractions based on dipolar mobilization across the glass-rubber relaxation revealed a finite rigid amorphous phase fraction for both the cold-crystallized specimens which was relatively insensitive to thermal history and degree of crystallinity (W{sub RAP}40.20).« less

The Role of Body Crystallization in Asteroidal Cores

NASA Astrophysics Data System (ADS)

Wasson, J. T.

1993-07-01

Large fractionations (factors of 2000-6000) in Ir/Ni and other ratios demonstrate that the magmatic groups of iron meteorites formed by fractional crystallization, and thus that the residual liquid remained well stirred during core crystallization. Past models have relied on solidification at the base or the top of the core, but body crystallization offers an attractive alternative. The simplest of the earlier models involved convective maxing induced by the liberation of heat and light elements (especially S) during upward crystallization from the center of the core. Other models involving downward crystallization from the core-mantle interface are based on the fact that temperatures at this location are slightly lower than those at the center; no whole-core stirring mechanism is provided by these models. Haack and Scott recently published a variant of the downward crystallization model involving the growth of giant (kilometer-scale) dendrites. Because crystallization creates a boundary layer enriched in S that does not participate in the convection, these models require several K of supercooling to induce crystallization (this undercooling is much greater than the temperature difference between the center of the core and the core-mantle interface). Buoyant forces will occasionally remove droplets of the basal boundary fluid; thus it was thinner and its degree of undercooling less than in that at the ceiling of the magma chamber. Homogeneous nucleation of metals is difficult to achieve; generally 200-300 K of undercooling is required, much more than could possibly occur in an asteroidal core. Crystals could, however, nucleate in the magma body on chromite, probably the first liquidus phase (A. Kracher, personal communication, notes that this is required to explain why Cr behaved like a compatible element despite having a solid/liquid D < 1). In addition, some tiny, submillimeter dendrites that formed at the top of the core must have pinched off and fallen into the magma. Such seeds settle as a result of buoyant forces (thus stirring the magma) and, as a result, achieve very thin boundary layers and require low degrees of undercooling in order to crystallize. The rate of core crystallization is limited by the rate of heat transport across the core-mantle interface. If sufficient nuclei are available at different sites, the bulk of the crystallization occurs where undercooling is least. It is possible that a larger fraction of the total crystallization occurred in the body of the magma than at its base or ceiling.

Synthesis and characterization of bulk metallic glasses prepared by laser direct deposition

NASA Astrophysics Data System (ADS)

Ye, Xiaoyang

Fe-based and Zr-based metallic glasses have attracted extensive interest for structural applications due to their excellent glass forming ability, superior mechanical properties, unique thermal and corrosion properties. In this study, the feasibility of synthesizing metallic glasses with good ductility by laser direct deposition is explored. Both in-situ synthesis with elemental powder mixture and ex-situ synthesis with prealloyed powder are discussed. Microstructure and properties of laser direct deposited metallic glass composites are analyzed. Synthesis of Fe-Cr-Mo-W-Mn-C-Si-B metallic glass composite with a large fraction of amorphous phase was accomplished using laser direct deposition. X-ray diffraction (XRD) and transmission electron microscopy investigations revealed the existence of amorphous structure. Microstructure analyses by optical microscopy and scanning electron microscopy (SEM) indicated the periodically repeated microstructures of amorphous and crystalline phases. Partially crystallized structure brought by laser reheating and remelting during subsequent laser scans aggregated in the overlapping area between each scan. XRD analysis showed that the crystalline particle embedded in the amorphous matrix was Cr 1.07Fe18.93 phase. No significant microstructural differences were found from the first to the last layer. Microhardness of the amorphous phase (HV0.2 1591) showed a much higher value than that of the crystalline phase (HV0.2 947). Macrohardness of the top layer had a value close to the microhardness of the amorphous region. Wear resistance property of deposited layers showed a significant improvement with the increased fraction of amorphous phase. Zr65Al10Ni10Cu15 amorphous composites with a large fraction of amorphous phase were in-situ synthesized by laser direct deposition. X-ray diffraction confirmed the existence of both amorphous and crystalline phases. Laser parameters were optimized in order to increase the fraction of amorphous phase. The microstructure analysis by scanning electron microscopy revealed the deposited structure was composed of periodically repeated amorphous and crystalline phases. Overlapping regions with nanoparticles aggregated were crystallized by laser reheating and remelting processes during subsequent laser scans. Vickers microhardness of the amorphous region showed around 35% higher than that of crystalline region. Average hardness obtained by a Rockwell macrohardness tester was very close to the microhardness of the amorphous region. The compression test showed that the fracture strain of Zr65Al10Ni10Cu15 amorphous composites was enhanced from less than 2% to as high as 5.7%, compared with fully amorphous metallic glass. Differential scanning calorimetry test results further revealed the amorphous structure and glass transition temperature Tg was observed to be around 655K. In 3 mol/L NaCl solution, laser direct deposited amorphous composites exhibited distinctly improved corrosion resistance, compared with fully-crystallized samples.

Igpet software for modeling igneous processes: examples of application using the open educational version

NASA Astrophysics Data System (ADS)

Carr, Michael J.; Gazel, Esteban

2017-04-01

We provide here an open version of Igpet software, called t-Igpet to emphasize its application for teaching and research in forward modeling of igneous geochemistry. There are three programs, a norm utility, a petrologic mixing program using least squares and Igpet, a graphics program that includes many forms of numerical modeling. Igpet is a multifaceted tool that provides the following basic capabilities: igneous rock identification using the IUGS (International Union of Geological Sciences) classification and several supplementary diagrams; tectonic discrimination diagrams; pseudo-quaternary projections; least squares fitting of lines, polynomials and hyperbolae; magma mixing using two endmembers, histograms, x-y plots, ternary plots and spider-diagrams. The advanced capabilities of Igpet are multi-element mixing and magma evolution modeling. Mixing models are particularly useful for understanding the isotopic variations in rock suites that evolved by mixing different sources. The important melting models include, batch melting, fractional melting and aggregated fractional melting. Crystallization models include equilibrium and fractional crystallization and AFC (assimilation and fractional crystallization). Theses, reports and proposals concerning igneous petrology are improved by numerical modeling. For reviewed publications some elements of modeling are practically a requirement. Our intention in providing this software is to facilitate improved communication and lower entry barriers to research, especially for students.

Trapped Melt in IIIAB Irons: Solid/Liquid Elemental Partitioning During the Fractionation of the IIIAB Magma

NASA Technical Reports Server (NTRS)

Wasson, John T.

1999-01-01

Group IIIAB, the largest iron-meteorite group, shows compositional trends (including a three-order-of-magnitude It concentration range) indicating that it formed by fractional crystallization of a metallic magma. Because about 200 irons are available, and all degrees of crystallization are well represented, IIIAB offers an excellent set of samples for the study of crystallization at all depths of the asteroidal core. On log-log Ir-Au, and Ir-As diagrams IIIAB forms a broad band; the breadth represents real meteorite-to-meteorite variations, far outside experimental or sampling uncertainties. A successful model must explain the width of this band; I suggest that it mainly resulted from the trapping of parental magma within the crystallizing solid. Because S is essentially insoluble in metal, the abundance of FeS is a measure of the fraction of trapped liquid. The trapped-melt model is supported by the observation that irons having higher S contents plot closer to the inferred composition of the magmatic parental liquid. The lowest S values are found in the irons occupying the left envelope of the IIIAB Ir-Au or Ir-As compositional fields, thus it is this set of irons that should be interpreted as the solid products of a fractionating magma. This simplifies the modeling of the crystallization process and allows inferences regarding the distribution ratios for other elements in the evolved IIIAB system. The large (multiton) Cape York irons show wide variations in their trapped-melt fractions; their compositions seem best understood in terms of a low initial S content of the IIIAB magma, about 20 mg/g. The inferred initial IIIAB distribution coefficient for Ir, 4.6, is much higher than published values based on laboratory studies of low-S systems; I suggest that low-S (and low-P) partition-ratio measurements tend to err in the direction of unity. In IIIAB distribution coefficients for Au, As, and Ni were still < 1 when the most evolved IIIAB irons formed, another indication of a low initial S content.

The Complex History of Alarcon Rise Mid-Ocean Ridge Rhyolite Revealed through Mineral Chemistry

NASA Astrophysics Data System (ADS)

Dreyer, B. M.; Portner, R. A.; Clague, D. A.; Daczko, N. R.; Castillo, P.; Bindeman, I. N.

2014-12-01

A suite of basalts to rhyolites recovered from the Alarcon Rise, the northern extension of the intermediate spreading-rate East Pacific Rise, provides an unparalleled test of established mechanisms for high-Si lava formation at ridges. Rhyolites are ≤35% phyric and poorly vesicular. Mafic xenoclasts are common, and plagioclase is the dominant phase. Olivine and clinopyroxene are also common, and orthopyroxene, FeTi-oxides, zircon, and rare pyrite blebs are present. Major and trace element glass data are consistent with MELTS models of fractional crystallization from a parental melt, but a diverse mineral population records added complexity. Olivine and plagioclase compositions are broadly consistent with models, with the exception of more variable Fo52-77 and An87-28 in a basaltic andesitic composition where pigeonite is predicted to replace olivine in the crystallizing assemblage between ~1085-1015°C; pigeonites analyzed in an andesite have lower Ca and Fe than predicted. Clinopyroxene variability generally increases with host melt SiO2, from Mg# 86-84 in basalts to Mg# 80-21 in rhyolites, and zoning is common with higher-MgO anhedral cores mantled by lower-MgO euhedral rims. Cooler magmas aided the preservation of disequilibrium and are supported by ~715-835°C Ti-in-zircon and ilmenite-magnetite thermometry in rhyolites. Despite a well-predicted liquid line of decent, multiple signals of chemical disequilibrium in intermediate to silicic melts support mixing of magmatic batches and/or assimilation of partially hydrous crust. Assimilation is permissible given δ18O values that are lower than expected solely from fractional crystallization (i.e., <6.3‰ at 77% SiO2), but assimilation extent is limited on the basis of δD ~82±8 and Pacific MORB-like 87Sr/86Sr. Zircon Hf-isotopes and trace element patterns support a juvenile oceanic crustal source. Whereas depleted Pacific MORB mantle source reservoir is supported by whole rock Sr-Nd isotopes, slight enrichments in zircon 176Hf/177Hf and whole rock 207,206Pb/204Pb may indicate an enriched MORB mantle component. In conclusion, mid-ocean rhyolite at Alarcon formed from a variety of petrogenetic processes including magma-mixing, assimilation, and crystallization following partial melting of slightly heterogeneous mantle source(s).

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

Li, XS; Michaelis, VK; Ong, TC

The controllable synthesis of well-ordered layered materials with specific nanoarchitecture poses a grand challenge in materials chemistry. Here the solvothermal synthesis of two structurally analogous 5-coordinate organosilicate complexes through a novel transesterification mechanism is reported. Since the polycrystalline nature of the intrinsic hypervalent Si complex thwarts the endeavor in determining its structure, a novel strategy concerning the elegant addition of a small fraction of B species as an effective crystal growth mediator and a sacrificial agent is proposed to directly prepare diffraction-quality single crystals without disrupting the intrinsic elemental type. In the determined crystal structure, two monomeric primary building unitsmore » (PBUs) self-assemble into a dimeric asymmetric secondary BU via strong Na+O2- ionic bonds. The designed one-pot synthesis is straightforward, robust, and efficient, leading to a well-ordered (10)-parallel layered Si complex with its principal interlayers intercalated with extensive van der Waals gaps in spite of the presence of substantial Na+ counter-ions as a result of unique atomic arrangement in its structure. However, upon fast pyrolysis, followed by acid leaching, both complexes are converted into two SiO2 composites bearing BET surface areas of 163.3 and 254.7m(2)g(-1) for the pyrolyzed intrinsic and B-assisted Si complexes, respectively. The transesterification methodology merely involving alcoholysis but without any hydrolysis side reaction is designed to have generalized applicability for use in synthesizing new layered metal-organic compounds with tailored PBUs and corresponding metal oxide particles with hierarchical porosity.« less

Statistical mechanics of two-dimensional shuffled foams: Geometry-topology correlation in small or large disorder limits

NASA Astrophysics Data System (ADS)

Durand, Marc; Kraynik, Andrew M.; van Swol, Frank; Käfer, Jos; Quilliet, Catherine; Cox, Simon; Ataei Talebi, Shirin; Graner, François

2014-06-01

Bubble monolayers are model systems for experiments and simulations of two-dimensional packing problems of deformable objects. We explore the relation between the distributions of the number of bubble sides (topology) and the bubble areas (geometry) in the low liquid fraction limit. We use a statistical model [M. Durand, Europhys. Lett. 90, 60002 (2010), 10.1209/0295-5075/90/60002] which takes into account Plateau laws. We predict the correlation between geometrical disorder (bubble size dispersity) and topological disorder (width of bubble side number distribution) over an extended range of bubble size dispersities. Extensive data sets arising from shuffled foam experiments, surface evolver simulations, and cellular Potts model simulations all collapse surprisingly well and coincide with the model predictions, even at extremely high size dispersity. At moderate size dispersity, we recover our earlier approximate predictions [M. Durand, J. Kafer, C. Quilliet, S. Cox, S. A. Talebi, and F. Graner, Phys. Rev. Lett. 107, 168304 (2011), 10.1103/PhysRevLett.107.168304]. At extremely low dispersity, when approaching the perfectly regular honeycomb pattern, we study how both geometrical and topological disorders vanish. We identify a crystallization mechanism and explore it quantitatively in the case of bidisperse foams. Due to the deformability of the bubbles, foams can crystallize over a larger range of size dispersities than hard disks. The model predicts that the crystallization transition occurs when the ratio of largest to smallest bubble radii is 1.4.

Mesozoic high-Mg andesites from the Daohugou area, Inner Mongolia: Upper-crustal fractional crystallization of parental melt derived from metasomatized lithospheric mantle wedge

NASA Astrophysics Data System (ADS)

Meng, Fanxue; Gao, Shan; Song, Zhaojun; Niu, Yaoling; Li, Xuping

2018-03-01

Mineral chemistry, major- and trace-element data, zircon U-Pb ages, and Sr-Nd isotopic data are presented for a suite of volcanic rocks from the Daohugou area, Ningcheng City, Inner Mongolia, on the northern margin of the North China Craton. Samples from the suite are of basaltic andesite to rhyolite in composition, with the rocks containing <60 wt% SiO2 have high MgO, Cr, and Ni contents, and classify as high-Mg andesites (HMAs). Zircons from a rhyolite yielded weighted mean 206Pb/238U age of 164 ± 1 Ma, indicating that the Daohugou volcanic suite is coeval with the Tiaojishan Formation of northern Hebei and western Liaoning Province. The HMAs have similar enriched-mantle I (EMI)-type isotopic compositions to each other, with low εNd (t) values, moderate (87Sr/86Sr) i ratios, enrichment in LREEs relative to LILEs, and depletion in HFSEs (e.g., Nb, Ta, Ti), indicating formation through protracted fractional crystallization of a common parental magma. The unusually low CaO contents and CaO/FeO ratios of olivine phenocrysts in the HMAs suggest that the parental melt was subduction-related. The results of Rhyolite-MELTS modelling indicates that HMAs may form through upper-crustal fractional crystallization from arc basalts. Therefore, the Daohugou HMAs were most likely formed through fractional crystallization of a parental melt derived from metasomatized lithospheric mantle at crustal depths. The addition of "water" to the cratonic keel may have played a key role in the destruction of the North China Craton.

Formation of thick stratiform Fe-Ti oxide layers in layered intrusion and frequent replenishment of fractionated mafic magma: Evidence from the Panzhihua intrusion, SW China

NASA Astrophysics Data System (ADS)

Song, Xie-Yan; Qi, Hua-Wen; Hu, Rui-Zhong; Chen, Lie-Meng; Yu, Song-Yue; Zhang, Jia-Fei

2013-03-01

Panzhihua intrusion is one of the largest layered intrusions that hosts huge stratiform Fe-Ti oxide layers in the central part of the Emeishan large igneous province, SW China. Up to 60 m thick stratiform massive Fe-Ti oxide layers containing 85 modal% of magnetite and ilmenite and overlying magnetite gabbro compose cyclic units of the Lower Zone of the intrusion. The cyclic units of the Middle Zone consist of magnetite gabbro and overlying gabbro. In these cyclic units, contents of Fe2O3(t), TiO2 and Cr and Fe3+/Ti4+ ratio of the rocks decrease upward, Cr content of magnetite and forsterite percentage of olivine decrease as well. The Upper Zone consists of apatite gabbro characterized by enrichment of incompatible elements (e.g., 12-18 ppm La, 20-28 ppm Y) and increasing of Fe3+/Ti4+ ratio (from 1.3 to 2.3) upward. These features indicate that the Panzhihua intrusion was repeatedly recharged by more primitive magma and evolved magmas had been extracted. Calculations using MELTS indicate that extensive fractionation of olivine and clinopyroxene in deep level resulted in increasing Fe and Ti contents in the magma. When these Fe-Ti-enriched magmas were emplaced along the base of the Panzhihua intrusion, Fe-Ti oxides became an early crystallization phase, leading to a residual magma of lower density. We propose that the unusually thick stratiform Fe-Ti oxide layers resulted from coupling of gravity settling and sorting of the crystallized Fe-Ti oxides from Fe-Ti-enriched magmas and frequent magma replenishment along the floor of the magma chamber.

Generation of felsic rocks of bimodal volcanic suites from thinned and rifted continental margins: Geochemical and Nd, Sr, Pb-isotopic evidence from Haida Gwaii, British Columbia, Canada

NASA Astrophysics Data System (ADS)

Dostal, Jaroslav; Hamilton, Tark S.; Shellnutt, J. Gregory

2017-11-01

The compositionally bimodal volcanic rocks of the Eocene-Miocene Masset Formation from Queen Charlotte basin, Haida Gwaii, British Columbia, Canada, underlie an area greater than 5000 km2 where their exposed sections are up to 1.6 km thick. The suite of mafic and felsic rocks (dacites and rhyolites) that erupted closely spaced in time, in both submarine and subaerial conditions, was associated with significant crustal extension and thin continental crust ( 19-24 km thick), with volcanism persisting for 35 Ma (from 46 to 11 Ma). Predominant mafic types (mafic:felsic 2:1) are moderately enriched mid-ocean-ridge-like basalts that were derived by a partial melting of a heterogeneous spinel peridotite source. Felsic rocks are plagioclase-phyric, two pyroxene-bearing, mainly peraluminous types which have Nd, Pb and Sr isotopic compositions overlapping those of basalts including high positive ƐNd(t) values (up to >+6). The chondrite-normalized REE patterns show light REE enrichment but flat heavy REE along with a variable negative Eu anomaly. Mineralogy, major and trace elements, Nd-Sr-Pb isotopic data and model calculations using MELTS are consistent with a derivation of felsic rocks from the basalts by fractional crystallization. The intercalation of basaltic and felsic rocks suggests the existence of separate, simultaneously active plumbing and feeder systems and relatively stable magma chamber(s) to generate large volumes of differentiated felsic magmas by fractional crystallization. The Masset rocks provide an example for the generation of felsic magmas of bimodal volcanic suites during rifting along a thinned continental margin. Appendix 1b Representative analyses of minerals of the Masset Formation felsic rocks

Preliminary morphological and X-ray diffraction studies of the crystals of the DNA cetyltrimethylammonium salt.

PubMed

Osica, V D; Pyatigorskaya, T L; Polyvtsev, O F; Dembo, A T; Kliya, M O; Vasilchenko, V N; Verkin, B I; Sukharevskya, B Y

1977-04-01

Double-stranded DNA molecules (molecular weight 2.5 X 10(5) - 5 X 10(5) daltons) have been crystallized from water-salt solutions as cetyltrimethylammonium salts (CTA-DNA). Variation of crystallization conditions results in a production of different types of CTA-DNA crystals: spherulits, dendrites, needle-shaped and faceted rhombic crystals, the latter beeing up to 0.3 mm on a side. X-ray diffraction data indicate that DNA molecules in the crystals form a hexagonal lattice which parameters vary slightly with the morphological type of the crystal. Comparison of the melting curves of the DNA preparation before and after crystallization suggests that DNA molecules are partially fractionated in the course of crystallization. Crystals of the CTA-DNA-proflavine complex have also been obtained.

Preliminary morphological and X-ray diffraction studies of the crystals of the DNA cetyltrimethylammonium salt.

PubMed Central

Osica, V D; Pyatigorskaya, T L; Polyvtsev, O F; Dembo, A T; Kliya, M O; Vasilchenko, V N; Verkin, B I; Sukharevskya, B Y

1977-01-01

Double-stranded DNA molecules (molecular weight 2.5 X 10(5) - 5 X 10(5) daltons) have been crystallized from water-salt solutions as cetyltrimethylammonium salts (CTA-DNA). Variation of crystallization conditions results in a production of different types of CTA-DNA crystals: spherulits, dendrites, needle-shaped and faceted rhombic crystals, the latter beeing up to 0.3 mm on a side. X-ray diffraction data indicate that DNA molecules in the crystals form a hexagonal lattice which parameters vary slightly with the morphological type of the crystal. Comparison of the melting curves of the DNA preparation before and after crystallization suggests that DNA molecules are partially fractionated in the course of crystallization. Crystals of the CTA-DNA-proflavine complex have also been obtained. Images PMID:866188

Large fraction of crystal directions leads to ion channeling

NASA Astrophysics Data System (ADS)

Nordlund, K.; Djurabekova, F.; Hobler, G.

2016-12-01

It is well established that when energetic ions are moving in crystals, they may penetrate much deeper if they happen to be directed in some specific crystal directions. This `channeling' effect is utilized for instance in certain ion beam analysis methods and has been described by analytical theories and atomistic computer simulations. However, there have been very few systematic studies of channeling in directions other than the principal low-index ones. We present here a molecular dynamics-based approach to calculate ion channeling systematically over all crystal directions, providing ion `channeling maps' that easily show in which directions channeling is expected. The results show that channeling effects can be quite significant even at energies below 1 keV, and that in many cases, significant planar channeling occurs also in a wide range of crystal directions between the low-index principal ones. In all of the cases studied, a large fraction (˜20 -60 % ) of all crystal directions show channeling. A practical implication of this is that modern experiments on randomly oriented nanostructures will have a large probability of channeling. It also means that when ion irradiations are carried out on polycrystalline samples, channeling effects on the results cannot a priori be assumed to be negligible. The maps allow for easy selection of good `nonchanneling' directions in experiments or alternatively finding wide channels for beneficial uses of channeling. We implement channeling theory to also give the fraction of channeling directions in a manner directly comparable to the simulations. The comparison shows good qualitative agreement. In particular, channeling theory is very good at predicting which channels are active at a given energy. This is true down to sub-keV energies, provided the penetration depth is not too small.

LOR-interleaving image reconstruction for PET imaging with fractional-crystal collimation

NASA Astrophysics Data System (ADS)

Li, Yusheng; Matej, Samuel; Karp, Joel S.; Metzler, Scott D.

2015-01-01

Positron emission tomography (PET) has become an important modality in medical and molecular imaging. However, in most PET applications, the resolution is still mainly limited by the physical crystal sizes or the detector’s intrinsic spatial resolution. To achieve images with better spatial resolution in a central region of interest (ROI), we have previously proposed using collimation in PET scanners. The collimator is designed to partially mask detector crystals to detect lines of response (LORs) within fractional crystals. A sequence of collimator-encoded LORs is measured with different collimation configurations. This novel collimated scanner geometry makes the reconstruction problem challenging, as both detector and collimator effects need to be modeled to reconstruct high-resolution images from collimated LORs. In this paper, we present a LOR-interleaving (LORI) algorithm, which incorporates these effects and has the advantage of reusing existing reconstruction software, to reconstruct high-resolution images for PET with fractional-crystal collimation. We also develop a 3D ray-tracing model incorporating both the collimator and crystal penetration for simulations and reconstructions of the collimated PET. By registering the collimator-encoded LORs with the collimator configurations, high-resolution LORs are restored based on the modeled transfer matrices using the non-negative least-squares method and EM algorithm. The resolution-enhanced images are then reconstructed from the high-resolution LORs using the MLEM or OSEM algorithm. For validation, we applied the LORI method to a small-animal PET scanner, A-PET, with a specially designed collimator. We demonstrate through simulated reconstructions with a hot-rod phantom and MOBY phantom that the LORI reconstructions can substantially improve spatial resolution and quantification compared to the uncollimated reconstructions. The LORI algorithm is crucial to improve overall image quality of collimated PET, which can have significant implications in preclinical and clinical ROI imaging applications.

Mechanisms of differentiation in the Skaergaard magma chamber

NASA Astrophysics Data System (ADS)

Tegner, C.; Lesher, C. E.; Holness, M. B.; Jakobsen, J. K.; Salmonsen, L. P.; Humphreys, M. C. S.; Thy, P.

2012-04-01

The Skaergaard intrusion is a superb natural laboratory for studying mechanisms of magma chamber differentiation. The magnificent exposures and new systematic sample sets of rocks that solidified inwards from the roof, walls and floor of the chamber provide means to test the relative roles of crystal settling, diffusion, convection, liquid immiscibility and compaction in different regions of the chamber and in opposite positions relative to gravity. Examination of the melt inclusions and interstitial pockets has demonstrated that a large portion of intrusion crystallized from an emulsified magma chamber composed of immiscible silica- and iron-rich melts. The similarity of ratios of elements with opposite partitioning between the immiscible melts (e.g. P and Rb) in wall, floor and roof rocks, however, indicate that large-scale separation did not occur. Yet, on a smaller scale of metres to hundred of metres and close to the interface between the roof and floor rocks (the Sandwich Horizon), irregular layers and pods of granophyre hosted by extremely iron-rich cumulates point to some separation of the two liquid phases. Similar proportions of the primocryst (cumulus) minerals in roof, wall and floor rocks indicate that crystal settling was not an important mechanism. Likewise, the lack of fractionation of elements with different behavior indicate that diffusion and fluid-driven metasomatism played relatively minor roles. Compositional convection and/or compaction within the solidifying crystal mush boundary layer are likely the most important mechanisms. A correlation of low trapped liquid fractions (calculated from strongly incompatible elements) in floor rocks with high fractionation density (the density difference between the crystal framework and the liquid) indicate that compaction is the dominating process in expelling evolved liquid from the crystal mush layer. This is supported by high and variable trapped liquid contents in the roof rocks, where gravity-driven compaction will not work.

Predicting the Mineral Composition of Dust Aerosols. Part 1; Representing Key Processes

NASA Technical Reports Server (NTRS)

Perlwitz, J. P.; Garcia-Pando, C. Perez; Miller, R. L.

2015-01-01

Soil dust aerosols created by wind erosion are typically assigned globally uniform physical and chemical properties within Earth system models, despite known regional variations in the mineral content of the parent soil. Mineral composition of the aerosol particles is important to their interaction with climate, including shortwave absorption and radiative forcing, nucleation of cloud droplets and ice crystals, heterogeneous formation of sulfates and nitrates, and atmospheric processing of iron into bioavailable forms that increase the productivity of marine phytoplankton. Here, aerosol mineral composition is derived by extending a method that provides the composition of a wet-sieved soil. The extension accounts for measurements showing significant differences between the mineral fractions of the wetsieved soil and the emitted aerosol concentration. For example, some phyllosilicate aerosols are more prevalent at silt sizes, even though they are nearly absent at these diameters in a soil whose aggregates are dispersed by wet sieving. We calculate the emitted mass of each mineral with respect to size by accounting for the disintegration of soil aggregates during wet sieving. These aggregates are emitted during mobilization and fragmentation of the original undispersed soil that is subject to wind erosion. The emitted aggregates are carried far downwind from their parent soil. The soil mineral fractions used to calculate the aggregates also include larger particles that are suspended only in the vicinity of the source. We calculate the emitted size distribution of these particles using a normalized distribution derived from aerosol measurements. In addition, a method is proposed for mixing minerals with small impurities composed of iron oxides. These mixtures are important for transporting iron far from the dust source, because pure iron oxides are more dense and vulnerable to gravitational removal than most minerals comprising dust aerosols. A limited comparison to measurements from North Africa shows that the model extensions result in better agreement, consistent with a more extensive comparison to global observations as well as measurements of elemental composition downwind of the Sahara, as described in companion articles.

Predicting the mineral composition of dust aerosols - Part 1: Representing key processes

NASA Astrophysics Data System (ADS)

Perlwitz, J. P.; Pérez García-Pando, C.; Miller, R. L.

2015-10-01

Soil dust aerosols created by wind erosion are typically assigned globally uniform physical and chemical properties within Earth system models, despite known regional variations in the mineral content of the parent soil. Mineral composition of the aerosol particles is important to their interaction with climate, including shortwave absorption and radiative forcing, nucleation of cloud droplets and ice crystals, heterogeneous formation of sulfates and nitrates, and atmospheric processing of iron into bioavailable forms that increase the productivity of marine phytoplankton. Here, aerosol mineral composition is derived by extending a method that provides the composition of a wet-sieved soil. The extension accounts for measurements showing significant differences between the mineral fractions of the wet-sieved soil and the emitted aerosol concentration. For example, some phyllosilicate aerosols are more prevalent at silt sizes, even though they are nearly absent at these diameters in a soil whose aggregates are dispersed by wet sieving. We calculate the emitted mass of each mineral with respect to size by accounting for the disintegration of soil aggregates during wet sieving. These aggregates are emitted during mobilization and fragmentation of the original undispersed soil that is subject to wind erosion. The emitted aggregates are carried far downwind from their parent soil. The soil mineral fractions used to calculate the aggregates also include larger particles that are suspended only in the vicinity of the source. We calculate the emitted size distribution of these particles using a normalized distribution derived from aerosol measurements. In addition, a method is proposed for mixing minerals with small impurities composed of iron oxides. These mixtures are important for transporting iron far from the dust source, because pure iron oxides are more dense and vulnerable to gravitational removal than most minerals comprising dust aerosols. A limited comparison to measurements from North Africa shows that the model extensions result in better agreement, consistent with a more extensive comparison to global observations as well as measurements of elemental composition downwind of the Sahara, as described in companion articles.

Determining Oxygen Isotopic Fractionation between the ferrous sulfate, melanterite, and aqueous sulfate

NASA Astrophysics Data System (ADS)

Shulaker, D. Z.; Kohl, I.; Coleman, M. L.

2011-12-01

Studying regions on Earth that are analogous to Mars serve as case studies for studying astrobiology and planetary surface rock formation processes. Rio Tinto, Spain is very rich in iron sulfates, and has an environment that is possibly very similar to the former environment on Mars. Certain bacteria play significant roles in accelerating pyrite oxidation rates, the products of which contribute to the formation of ferrous sulfates, such as melanterite. During mineral crystallization in an aqueous solution, there are systematic isotopic differences between dissolved species and solid phases. Quantifying this fractionation enables isotopic analysis to be used to trace the original isotopic signature of the dissolved species. Isotope fractionation has been determined for minerals such as gypsum and epsomite, and from these results and theoretical predictions, it is expected that melanterite, a mineral potentially found on Mars, would be more enriched in oxygen-18 relative to the aqueous solution from which it crystallized.Thus, determining the oxygen-18 isotopic fractionation between melanterite and dissolved sulfate has many potential benefits for understanding surface processes on Mars and its past environment. To investigate the oxygen isotope fractionation for melanterite, acidic aqueous solutions saturated with dissolved hydrated ferrous sulfate were evaporated at 25 deg C and 40 deg C and under different conditions to induce different evaporation rates. During evaporation, the aqueous solution and crystallized melanterite were sampled at different stages. Oxygen-18 isotopic compositions were then measured. However, the fractionations observed in the experiments were opposite from predictions. At 25 deg C without enhanced evaporation, the dissolved sulfate was +5.5 per mil relative to the solid, while at 40 deg C it was +4.3 per mil. With enhanced evaporation, fractionation was +2.1 per mil, while at 40 deg C it was +3.6 per mil. In addition, at 40 deg C, evaporation rates and fractionation were larger than at 25 deg C. Because no Rayleigh fractionation was observed, this system was not in equilibrium, and was most likely dominated by kinetics. Because of the unexpected results, further research will be conducted on the oxygen isotope fractionation of melanterite.

Crystallization and X-ray analysis of the T = 4 particle of hepatitis B capsid protein with an N-terminal extension

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

Tan, Wen Siang; McNae, Iain W.; Ho, Kok Lian

2007-08-01

Hepatitis B virus capsids have significant potential as carriers for immunogenic peptides. The crystal structure of the T = 4 particle of hepatitis B core protein containing an N-terminal extension reveals that the fusion peptide is exposed on the exterior of the particle. Hepatitis B core (HBc) particles have been extensively exploited as carriers for foreign immunological epitopes in the development of multicomponent vaccines and diagnostic reagents. Crystals of the T = 4 HBc particle were grown in PEG 20 000, ammonium sulfate and various types of alcohols. A temperature jump from 277 or 283 to 290 K was foundmore » to enhance crystal growth. A crystal grown using MPD as a cryoprotectant diffracted X-rays to 7.7 Å resolution and data were collected to 99.6% completeness at 8.9 Å. The crystal belongs to space group P2{sub 1}2{sub 1}2{sub 1}, with unit-cell parameters a = 352.3, b = 465.5, c = 645.0 Å. The electron-density map reveals a protrusion that is consistent with the N-terminus extending out from the surface of the capsid. The structure presented here supports the idea that N-terminal insertions can be exploited in the development of diagnostic reagents, multicomponent vaccines and delivery vehicles into mammalian cells.« less

Practical macromolecular cryocrystallography

PubMed Central

Pflugrath, J. W.

2015-01-01

Cryocrystallography is an indispensable technique that is routinely used for single-crystal X-ray diffraction data collection at temperatures near 100 K, where radiation damage is mitigated. Modern procedures and tools to cryoprotect and rapidly cool macromolecular crystals with a significant solvent fraction to below the glass-transition phase of water are reviewed. Reagents and methods to help prevent the stresses that damage crystals when flash-cooling are described. A method of using isopentane to assess whether cryogenic temperatures have been preserved when dismounting screened crystals is also presented. PMID:26057787

Chemical variation and fractionation of KREEP basalt magmas

NASA Technical Reports Server (NTRS)

Irving, A. J.

1977-01-01

The fact that 53 Apollo 15 igneous KREEP basalts show a range of 100 Mg/(Mg + Fe) from 73 to 35, and that there are systematic variations in K2O and trace element abundances with the Mg/(Mg + Fe) ratio, suggests that the KREEP basalts are a magma series generated by fractional crystallization processes. Experimental and chemical evidence indicate that this magma series results from low-pressure, possibly subvolcanic, fractional crystallization of a magnesian parental liquid (100 Mg/(Mg + Fe) equal to approximately 72) by removal of low-Ca pyroxene and plagioclase, with eventual production of liquids similar in composition to 15405 quartz-monozodiorites. One soil sample, SAO 465-11, corresponds to the postulated parental liquid, which might have been a direct partial melt of troctolitic materials in the deep lunar crust.

76 FR 5216 - Florida Power Corporation, Crystal River Unit 3 Nuclear Generating Plant; Exemption

Federal Register 2010, 2011, 2012, 2013, 2014

2011-01-28

... for Crystal River from 24 to 26 months on a one-time only basis. The proposed exemption does not make... licensed operator requalification program period for Crystal River from 24 to 26 months on a one-time only....59, by allowing Crystal River a one-time extension in the allowed time for completing the current...

Association of Ions and Fractional Crystallization.

ERIC Educational Resources Information Center

Scaife, Charles W. J.; Dubs, Richard L.

1983-01-01

Presents an experiment in which color is used as an additional characteristic when purifying and identifying crystals of two soluble salts obtained from a metathesis reaction. Indicates that the experiment has been used with both nonmajors and inorganic chemistry students in at least their third term. (JN)

Interpretation of open system petrogenetic processes: Phase equilibria constraints on magma evolution

NASA Astrophysics Data System (ADS)

Defant, Marc J.; Nielsen, Roger L.

1990-01-01

We have used a computer model (TRACES) to simulate low pressure differentiation of natural basaltic magmas in an attempt to investigate the chemical dynamics of open system magmatic processes. Our results, in the form of simulated liquid lines of descent and the calculated equilibrium mineralogy, were determined for perfect fractional crystallization; fractionation paired with recharge and eruption (PRF); fractionation paired with assimilation (AFC); and fractionation paired with recharge, eruption, and assimilation (FEAR). These simulations were calculated in an attempt to assess the effects of combinations of petrogenetic processes on major and trace element evolution of natural systems and to test techniques that have been used to decipher the relative roles of these processes. If the results of PRF calculations are interpreted in terms of a mass balance based fractionation model (e.g., Bryan et al., 1969), it is possible to generate low residuals even if one assumes that fractional crystallization was the only active process. In effect, the chemical consequences of recharge are invisible to mass balance models. Pearce element ratio analyses, however, can effectively discern the effects of PRF versus simple fractionation. The fractionating mineral proportions, and therefore, bulk distribution coefficients ( D¯) of a differentiating system are dependent on the recharge or assimilation rate. Comparison of the results of simulations assuming constant D¯ with the results calculated by TRACES show that the steady state liquid concentrations of some elements can differ by a factor of 2 to 5. If the PRF simulation is periodic, with episodes of mixing separated by intervals of fractionation, parallel liquidus mineral control lines are produced. Most of these control lines do not project back to the parental composition. This must be an important consideration when attempting to calculate a potential parental magma for any natural suite where magma chamber recharge has occurred. Most basaltic magmas cannot evolve to high silica compositions without magnetite fractionation. Small amounts of rhyolite assimilation (assimilation/fractionation < 0.1), however, can drive evolving basalts to more silica rich compositions. If mass balance models are used to interpret these synthetic AFC data, low residuals are obtained if magnetite is added to the crystallizing assemblage. This approach works even for cases where magnetite was not a fractionating phase. Thus, the mass balance results are mathematically correct, but are geologically irrelevant.

CRYSTALLINE PNEUMOCOCCUS ANTIBODY

PubMed Central

Northrop, John H.; Goebel, Walther F.

1949-01-01

1. The immune precipitate formed by antipneumococcus horse serum and the specific polysaccharide is not hydrolyzed by trypsin as is the diphtheria toxin-antitoxin complex, and purified pneumococcus antibody cannot be isolated by the method used for the isolation and crystallization of diphtheria antitoxin. 2. Type I pneumococcus antibody, completely precipitable by Type I polysaccharide, may be obtained from immune horse serum globulin by precipitation of the inert proteins with acid potassium phthalate. 3. The antibody obtained in this way may be fractionated by precipitation with ammonium sulfate into three main parts. One is insoluble in neutral salts but soluble from pH 4.5 to 3.0 and from pH 9.5 to 10.5. This is the largest fraction. A second fraction is soluble in 0.05 to 0.2 saturated ammonium sulfate and the third fraction is soluble in 0.2 saturated ammonium sulfate and precipitated by 0.35 saturated ammonium sulfate. The second fraction can be further separated by precipitation with 0.17 saturated ammonium sulfate to yield a small amount of protein which is soluble in 0.17 saturated ammonium sulfate but insoluble in 0.25 saturated ammonium sulfate. This fraction crystallizes in poorly formed, rounded rosettes. 4. The crystallization does not improve the purity of the antibody and is accompanied by the formation of an insoluble protein as in the case of diphtheria antitoxin. 5. None of the fractions obtained is even approximately homogeneous as determined by solubility measurements. 6. Purified antibody has also been obtained by dissociating the antigen-antibody complex. 7. The protective value of the fractions is quite different; that of the dissociated antibody being the highest and that of the insoluble fraction, the lowest. 8. All the fractions are immunologically specific since they do not precipitate with Type II polysaccharide nor protect against Type II pneumococci. 9. All the fractions give a positive precipitin reaction with antihorse rabbit serum. The dissociated antibody gives the least reaction. 10. Comparison of the various fractions, either by their solubility in salt solution or through immunological reactions, indicates that there are a large number of proteins present in immune horse serum, all of which precipitate with the specific polysaccharide but which have very different protective values, different reactions with antihorse rabbit serum, and different solubility in salt solutions. PMID:18131872

75 FR 49865 - Extension of Comment Period; Airplane and Engine Certification Requirements in Supercooled Large...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-08-16

... Ice Crystal Icing Conditions AGENCY: Federal Aviation Administration (FAA), DOT. ACTION: Notice of... airplanes most affected by these icing conditions, mixed phase and ice crystal conditions for all transport category airplanes, and supercooled large drop, mixed phase, and ice crystal icing conditions for all...

Evaluating Fluid and Crystallized Abilities in the Performance of an Educational Process

ERIC Educational Resources Information Center

Blanch, Angel

2015-01-01

The fluid and crystallized ("Gf-Gc") intelligence theory has been used extensively to evaluate the influence of cognitive abilities on educational outcomes within cross-sectional and longitudinal research designs. This study evaluated the contribution of fluid and crystallized abilities in the performance of a 1-week instructional…

Investigation of magnesium isotope fractionation during basalt differentiation: Implications for a chondritic composition of the terrestrial mantle

USGS Publications Warehouse

Teng, F.-Z.; Wadhwa, M.; Helz, R.T.

2007-01-01

To investigate whether magnesium isotopes are fractionated during basalt differentiation, we have performed high-precision Mg isotopic analyses by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) on a set of well-characterized samples from Kilauea Iki lava lake, Hawaii, USA. Samples from the Kilauea Iki lava lake, produced by closed-system crystal-melt fractionation, range from olivine-rich cumulates to highly differentiated basalts with MgO content ranging from 2.37 to 26.87??wt.%. Our results demonstrate that although these basalts have diverse chemical compositions, mineralogies, crystallization temperatures and degrees of differentiation, their Mg isotopic compositions display no measurable variation within the limits of our external precision (average ??26Mg = - 0.36 ?? 0.10 and ??25Mg = - 0.20 ?? 0.07; uncertainties are 2SD). This indicates that Mg isotopic fractionation during crystal-melt fractionation at temperatures of ??? 1055????C is undetectable at the level of precision of the current investigation. Calculations based on our data suggest that at near-magmatic temperatures the maximum fractionation in the 26Mg/24Mg ratio between olivine and melt is 0.07???. Two additional oceanic basalts, two continental basalts (BCR-1 and BCR-2), and two primitive carbonaceous chondrites (Allende and Murchison) analyzed in this study have Mg isotopic compositions similar to the Kilauea Iki lava lake samples. In contrast to a recent report [U. Wiechert, A.N. Halliday, Non-chondritic magnesium and the origins of the inner terrestrial planets, Earth and Planetary Science Letters 256 (2007) 360-371], the results presented here suggest that the Bulk Silicate Earth has a chondritic Mg isotopic composition. ?? 2007.

Potassium isotope variations in forearc boninite-series volcanics from Chichijima

NASA Astrophysics Data System (ADS)

Parendo, C. A.; Jacobsen, S. B.; Yamashita, K.; Okano, O.

2017-12-01

Variability in the K content of arc lavas is related to fundamental processes. These include (1) the transfer of material from the subducting slab to the mantle wedge, (2) melting occurring within the mantle wedge, and (3) differentiation processes, such as fractional crystallization, which greatly modify the compositions of magma bodies that erupt arc lavas. To explore these processes, samples from Chichijima, an island that is part of the Izu-Bonin forearc, were analyzed for 41K/39K ratios. Analyses were made using an Isoprobe-P MC-ICPMS equipped with a hexapole collision and reaction cell. Precisions obtained were typically about 0.05 ‰ (2SE). We have acquired 41K/39K ratios from eight samples. 41K/39K ratios are reported relative to an estimate of Bulk Silicate Earth. Six of the analyzed samples have 41K/39K ratios that span a range between -0.01 and -0.48 ‰. One sample has a much higher value, +0.44 ‰, and one a much lower value, -1.38 ‰. The samples are variably differentiated, with MgO content ranging approximately from 17 to 1 wt. %. An apparent trend is observed in which the most primitive lavas have 41K/39K ratios near 0.0 ‰ and more evolved lavas have more negative values. A working hypothesis is that 41K/39K ratios vary among these samples because of fractional crystallization. However, multiple other processes need to be considered, including, for some samples, possible post-emplacement alteration. If fractional crystallization is controlling 41K/39K ratios, this requires a precipitating mineral that both incorporates a substantial amount of K and fractionates 41K/39K ratios. Minerals that potentially meet these criteria include feldspars and micas. Effects on 41K/39K ratios may become more pronounced during the later stages of differentiation, when precipitating minerals incorporate more K. Further study will test this hypothesis and explore which minerals may be causing isotopic fractionation. If the fractional crystallization effects can be understood, then it should also be possible to see through these effects and estimate the 41K/39K ratios of the parental magmas.

The effect of crystal shape, size and bimodality on the maximum packing and the rheology of crystal bearing magma

NASA Astrophysics Data System (ADS)

Moitra, Pranabendu; Gonnermann, Helge

2014-05-01

Magma often contains crystals of various shapes and sizes. We present experimental results on the effect of the shape- and size-distribution of solid particles on the rheological properties of solid-liquid suspensions, which are hydrodynamically analogous to crystal-bearing magmas. The suspensions were comprised of either a single particle shape and size (unimodal) or a mixture of two different particle shapes and sizes (bimodal). For each type of suspension we characterized the dry maximum packing fraction of the particle mixture using the tap density method. We then systematically varied the total volume fraction of particles in the suspension, as well as the relative proportion of the two different particle types in the bimodal suspensions. For each of the resultant mixtures (suspensions) we performed controlled shear stress experiments using a rotational rheometer in parallel-plate geometry spanning 4 orders of magnitude in shear stress. The resultant data curves of shear stress as a function of shear rate were fitted using a Herschel-Bulkley rheological model. We find that the dry maximum packing decreases with increasing particle aspect ratio (ar) and decreasing particle size ratio (Λ). The highest dry maximum packing was obtained at 60-75% volume of larger particles for bimodal spherical particle mixture. Normalized consistency, Kr, defined as the ratio of the consistency of the suspension and the viscosity of the suspending liquid, was fitted using a Krieger-Dougherty model as a function of the total solid volume fraction (φ). The maximum packing fractions (φm) obtained from the shear experimental data fitting of the unimodal suspensions were similar in magnitude with the dry maximum packing fractions of the unimodal particles. Subsequently, we used the dry maximum packing fractions of the bimodal particle mixtures to fit Kr as a function of φ for the bimodal suspensions. We find that Kr increases rapidly for suspensions with larger ar and smaller Λ. We also find that both the apparent yield stress and the shear thinning behavior of the suspensions increase with increasing ar and become significant at φ/φm ≥ 0.4.

The origin and evolution of silicic magmas during continental rifting: new constraints from trace elements and oxygen isotopes from Ethiopian volcanoes

NASA Astrophysics Data System (ADS)

Hutchison, W.; Boyce, A.; Mather, T. A.; Pyle, D. M.; Yirgu, G.; Gleeson, M. L.

2017-12-01

The petrologic diversity of rift magmas is generated by two key processes: interaction with the crust via partial melting or assimilation; and closed-system fractional crystallization of the parental magma. It is not yet known whether these two petrogenetic processes vary spatially between different rift settings, and whether there are any significant secular variations during rift evolution. The Ethiopian Rift is the ideal setting to test these hypotheses because it captures the transition from continental rifting to sea-floor spreading and has witnessed the eruption of large volumes of mafic and silicic volcanic rocks since 30 Ma. We use new oxygen isotope (δ18O) and trace element data to fingerprint fractional crystallisation and partial crustal melting processes in Ethiopia and evaluate spatial variations between three active rift segments. δ18O measurements are used to examine partial crustal melting processes. We find that most δ18O data from basalts to rhyolites fall within the bounds of modelled fractional crystallization trajectories (i.e., 5.5-6.5 ‰). Few samples deviate from this trend, emphasising that fractional crystallization is the dominant petrogenetic processes and that little fusible Precambrian crustal material (δ18O of 7-18 ‰) remain to be assimilated beneath the magmatic segments. Trace element systematics (e.g., Ba, Sr, Rb, Th and Zr) further underscore the dominant role of fractional crystallization but also reveal important variations in the degree of melt evolution between the volcanic systems. We find that the most evolved silicic magmas, i.e., those with greatest peralkalinity (molar Na2O+K2O>Al2O3), are promoted in regions of lowest magma flux off-axis and along rift. Our findings provide new information on the nature of the crust beneath Ethiopia's active magmatic segments and also have relevance for understanding ancient rift zones and the geotectonic settings that promote genesis of economically-valuable mineral deposits.

Basalt generation at the Apollo 12 site. Part 2: Source heterogeneity, multiple melts, and crustal contamination

NASA Technical Reports Server (NTRS)

Neal, Clive R.; Hacker, Matthew D.; Snyder, Gregory A.; Taylor, Lawrence A.; Liu, Yun-Gang; Schmitt, Roman A.

1994-01-01

The petrogenesis of Apollo 12 mare basalts has been examined with emphasis on trace-element ratios and abundances. Vitrophyric basalts were used as parental compositions for the modeling, and proportions of fractionating phases were determined using the MAGFOX prograqm of Longhi (1991). Crystal fractionation processes within crustal and sub-crustal magma chambers are evaluated as a function of pressure. Knowledge of the fractionating phases allows trace-element variations to be considered as either source related or as a product of post-magma-generation processes. For the ilmenite and olivine basalts, trace-element variations are inherited from the source, but the pigeonite basalt data have been interpreted with open-system evolution processes through crustal assimilation. Three groups of basalts have been examined: (1) Pigeonite basalts-produced by the assimilation of lunar crustal material by a parental melt (up to 3% assimilation and 10% crystal fractionation, with an 'r' value of 0.3). (2) Ilmenite basalts-produced by variable degrees of partial melting (4-8%) of a source of olivine, pigeonite, augite, and plagioclase, brought together by overturn of the Lunar Magma Ocean (LMO) cumulate pile. After generation, which did not exhaust any of the minerals in the source, these melts experienced closed-system crystal fractionation/accumulation. (3) Olivine basalts-produced by variable degrees of partial melting (5-10%) of a source of olivine, pigeonite, and augite. After generation, again without exhausting any of the minerals in the source, these melts evolved through crystal accumulation. The evolved liquid counterparts of these cumulates have not been sampled. The source compositions for the ilmenite and olivine basalts were calculated by assuming that the vitrophyric compositions were primary and the magmas were produced by non-modal batch melting. Although the magnitude is unclear, evaluation of these source regions indicates that both be composed of early- and late-stage Lunar Magma Ocean (LMO) cumulates, requiring an overturn of the cumulate pile.

Formation of the Structure of a Eutectic Alloy of the Nb - Si System During Directed Crystallization with Liquid-Metal Coolant

NASA Astrophysics Data System (ADS)

Bondarenko, Yu. A.; Echin, A. B.; Kolodyazhnyi, M. Yu.; Surova, V. A.

2017-11-01

Peculiarities of the structure of a refractory eutectic alloy of the Nb - Si system, formed by the method of directed crystallization with liquid-metal coolant, have been studied. Characteristic zones of microstructure of the ingot obtained upon directed crystallization are considered, the alloy composition is analyzed, and volume fractions of phases in the Nb - Si composite are determined.

Evaluating crustal contributions to enriched shergottites from the petrology, trace elements, and Rb-Sr and Sm-Nd isotope systematics of Northwest Africa 856

NASA Astrophysics Data System (ADS)

Ferdous, J.; Brandon, A. D.; Peslier, A. H.; Pirotte, Z.

2017-08-01

The origin of the incompatible trace element (ITE) characteristics of enriched shergottites has been critical for examining two contradicting scenarios to explain how these Martian meteorites form. The first scenario is that it reflects ITE enrichment in an early-formed mantle reservoir whereas the second scenario attributes it to assimilation of ancient Martian crust (∼4-4.5 Ga) by ITE-depleted magmas. Strongly differentiated shergottite magmas may yield added constraints for determining which scenario can best explain this signature in enriched shergottites. The meteorite Northwest Africa (NWA) 856 is a basaltic shergottite that, unlike many enriched shergottites, lacks olivine and has undergone extensive differentiation from more primitive parent magma. In similarity to other basaltic shergottites, NWA 856 is comprised primarily of compositionally zoned clinopyroxenes (45% pigeonite and 23% augite), maskelynite (23%) and accessory minerals such as ulvöspinel, merrillite, Cl-apatite, ilmenite, pyrrhotite, baddeleyite and silica polymorph. The CI-chondrite normalized rare earth element (REE) abundance patterns for its maskelynite, phosphates, and its whole rock are flat with corresponding light-REE depletions in clinopyroxenes. The 87Rb-87Sr and 147Sm-143Nd internal isochron ages are 162 ± 14 (all errors are ±2σ) Ma and 162.7 ± 5.5 Ma, respectively, with an initial εNdI = -6.6 ± 0.2. The Rb-Sr isotope systematics are affected by terrestrial alteration resulting in larger scatter and a less precise internal isochron age. The whole rock composition is used in MELTS simulations to model equilibrium and fractional crystallization sequences to compare with the crystallization sequence from textural observations and to the mineral compositions. These models constrain the depth of initial crystallization to a pressure range of 0.4-0.5 GPa (equivalent to 34-42 km) in anhydrous conditions at the Fayalite-Magnetite-Quartz buffer, and consistently reproduce the observed mineralogy throughout the sequence with progressive crystallization. The Ti/Al ratios in the clinopyroxenes are consistent with initial crystallization occurring at these depths followed by polybaric crystallization as the parent magma ascended to the surface. The REE abundances in the clinopyroxenes and maskelynite are consistent with progressive crystallization in a closed system. The new results for NWA 856 are combined with other shergottite data and are compared to mixing and assimilation and fractional crystallization (AFC) models using depleted shergottite magmas and ancient Martian crust as end-members. The models indicate that the range of REE abundances and ratios, when taken in isolation, can be successfully explained for all shergottites by crustal contamination. However, no successful crustal contamination model can explain the restricted εNdI of -6.8 ± 0.2 over the wide range of Mg# (0.65-0.25), and corresponding trace element variations from enriched shergottites to depleted shergottites. The findings indicate that the origin of the long-term ITE-enriched signature in enriched shergottites and the geochemical variability seen in shergottites is not a result of crustal contamination but instead reflects ancient mantle heterogeneity.

Tetragonal Lysozyme Nucleation and Crystal Growth: The Role of the Solution Phase

NASA Technical Reports Server (NTRS)

Pusey, Marc L.; Forsythe, Elizabeth; Sumida, John; Maxwell, Daniel; Gorti, Sridhar; Curreri, Peter A. (Technical Monitor)

2002-01-01

Experimental evidence indicates a dominant role of solution phase interactions in nucleating and growing tetragonal lysozyme crystals. These interactions are extensive, even at saturation, and may be a primary cause of misoriented regions in crystals grown on Earth. Microgravity, by limiting interfacial concentrations to diffusion-controlled levels, may benefit crystal quality by also reducing the extent of associated species present at the interface.

Partitioning of zinc among common ferromagnesian minerals and implications for hydrothermal mobilization

USGS Publications Warehouse

Johnson, C.A.

1994-01-01

In systems where metals are scavenging from crystalline rocks by through-flowing fluids, the important host minerals must be dissolved or must undergo cation-exchange reactions with the fluid. Whereas copper resides in sulfides, zinc resides in magnetic and, to a lesser extent, in biotite, clinopyroxene and olivine. Magnetite is known from petrographic studies to be more resistant to alteration than sulfides. For metals extracted from crystalline rocks, the Cu:Zn mass ratio may thus decrease with progressive alteration. In systems where metals are scavenged from cooling magmas by exsolving fluids, the metals are partitioned among melt, fluid and any crystals that have fractionated. For zinc, crystal fractionation may be an important sink if magnetite or biotite crystallize before fluid saturation. The zinc concentrations of magmatic fluids will thus be reduced. -from Author

Purification, identification and preliminary crystallographic studies of an allergenic protein from Lathyrus sativus

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

Qureshi, Insaf A.; Sethi, Dhruv K.; Salunke, Dinakar M., E-mail: dinakar@nii.res.in

2006-09-01

A 24 kDa protein was purified from the seeds of L. sativus by ammonium sulfate fractionation and ion-exchange chromatography. Crystals were obtained by the hanging-drop vapour-diffusion method. A 24 kDa protein was purified from the seeds of Lathyrus sativus by ammonium sulfate fractionation and ion-exchange chromatography. The N-terminal amino-acid sequence showed significant homology with the 2S albumin class of seed storage proteins. The protein showed 85% sequence homology with the seed albumin of Pisum sativum within the 40 N-terminal residues. Crystals were obtained by the hanging-drop vapour-diffusion method. The crystals belonged to space group P2{sub 1}2{sub 1}2{sub 1}, with unit-cellmore » parameters a = 43.5, b = 82.7, c = 153.4 Å.« less

The Petrographic Distinction between Basalt and Andesite Based upon the Arrested Fractionation of Plagioclase Phenocrysts.

ERIC Educational Resources Information Center

Garlick, G. Donald; Garlick, Benjamin J.

1987-01-01

Discusses the need to take into account the effects of arrested fractional crystallization in the petrographic classification of volcanic rocks containing plagioclase phenocrysts. Describes the development and use of a computer program to accomplish this task graphically. (TW)

Basalt-Trachybasalt Fractionation in Gale Crater, Mars

NASA Astrophysics Data System (ADS)

Bridges, J. C.; Edwards, P. H.; Filiberto, J.; Schwenzer, S. P.; Gasda, P.; Wiens, R.

2016-08-01

A set of igneous float rocks in Gale Crater have been analysed by ChemCam. They are basalt-trachybasalts, 47 to 53 ± 5 wt% SiO2 and formed by ol-dominated crystal fractionation from an Adirondack type basalt, in magmatism with tholeiitic affinities.

Diffusion-controlled magnesium isotopic fractionation of a single crystal forsterite evaporated from the solid state

NASA Technical Reports Server (NTRS)

Wang, Jianhua; Davis, Andrew M.; Hashimoto, Akihiko; Clayton, Robert N.

1993-01-01

Though the origin of calcium- and aluminum-rich inclusions (CAI's) in carbonaceous chondrites is till a disputed issue, evaporation is no doubt one of the most important processes for the formation of CAI's in the early solar nebula. The mechanism for production of large isotopic mass fractionation effects in magnesium, silicon, oxygen, and chromium in CAI's can be better understood by examining isotopic fractionation during the evaporation of minerals. New evaporation experiments were performed on single-crystal forsterite. The magnesium isotopic distribution near the evaporating surfaces of the residues using a modified AEI IM-20 ion microprobe to obtain rastered beam depth profiles was measured. A theoretical model was used to explain the profiles and allowed determination of the diffusion coefficient of Mg(++) in forsterite at higher temperatures than previous measurements. The gas/solid isotopic fractionation factor for magnesium for evaporation from solid forsterite was also determined and found to be nearly the same as that for evaporation of liquid Mg2SiO4.

Premature melt solidification during mold filling and its influence on the as-cast structure

NASA Astrophysics Data System (ADS)

Wu, M.; Ahmadein, M.; Ludwig, A.

2018-03-01

Premature melt solidification is the solidification of a melt during mold filling. In this study, a numerical model is used to analyze the influence of the pouring process on the premature solidification. The numerical model considers three phases, namely, air, melt, and equiaxed crystals. The crystals are assumed to have originated from the heterogeneous nucleation in the undercooled melt resulting from the first contact of the melt with the cold mold during pouring. The transport of the crystals by the melt flow, in accordance with the socalled "big bang" theory, is considered. The crystals are assumed globular in morphology and capable of growing according to the local constitutional undercooling. These crystals can also be remelted by mixing with the superheated melt. As the modeling results, the evolutionary trends of the number density of the crystals and the volume fraction of the solid crystals in the melt during pouring are presented. The calculated number density of the crystals and the volume fraction of the solid crystals in the melt at the end of pouring are used as the initial conditions for the subsequent solidification simulation of the evolution of the as-cast structure. A five-phase volume-average model for mixed columnar-equiaxed solidification is used for the solidification simulation. An improved agreement between the simulation and experimental results is achieved by considering the effect of premature melt solidification during mold filling. Finally, the influences of pouring parameters, namely, pouring temperature, initial mold temperature, and pouring rate, on the premature melt solidification are discussed.

Classification of igneous rocks analyzed by ChemCam at Gale crater, Mars

DOE PAGES

Cousin, Agnes; Sautter, Violaine; Payré, Valérie; ...

2017-02-09

Several recent studies have revealed that Mars is not a simple basalt-covered planet, but has a more complex geological history. In Gale crater on Mars, the Curiosity rover discovered 59 igneous rocks. This article focuses on their textures (acquired from the cameras such as MAHLI and MastCam) and their geochemical compositions that have been obtained using the ChemCam instrument. Light-toned crystals have been observed in most of the rocks. They correspond to feldspars ranging from andesines/oligoclases to anorthoclases and sanidines in the leucocratic vesiculated rocks. Darker crystals observed in all igneous rocks (except the leucocratic vesiculated ones) were analyzed bymore » LIBS and mainly identified as Fe-rich pigeonites and Fe-augites. Iron oxides have been observed in all groups whereas F-bearing minerals have been detected only in few of them. From their textural analysis and their whole-rock compositions, all these 59 igneous rocks have been classified in five different groups; from primitive rocks i.e. dark aphanitic basalts/basanites, trachybasalts, tephrites and fine/coarse-grained gabbros/norites to more evolved materials i.e. porphyritic trachyandesites, leucocratic trachytes and quartz-diorites. The basalts and gabbros are found all along the traverse of the rover, whereas the felsic rocks are located before the Kimberley formation, i.e. close to the Peace Vallis alluvial fan deposits. This suggests that these alkali rocks have been transported by fluvial activity and could come from the Northern rim of the crater, and may correspond to deeper strata buried under basaltic regolith (Sautter et al., 2015). Some of the basaltic igneous rocks are surprisingly enriched in iron, presenting low Mg# similar to the nakhlite parental melt that cannot be produced by direct melting of the Dreibus and Wanke (1986) martian primitive mantle. The basaltic rocks at Gale are thus different from Gusev basalts. They could originate from different mantle reservoirs, or they could have undergone a more extensive fractional crystallization. Lastly, Gale basaltic rocks could have been the parental magma of residual liquid extending into alkali field towards trachyte composition as magma fractionated under anhydrous condition on its way to the surface before sub adiabatic ascent.« less

Classification of igneous rocks analyzed by ChemCam at Gale crater, Mars

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

Cousin, Agnes; Sautter, Violaine; Payré, Valérie

Several recent studies have revealed that Mars is not a simple basalt-covered planet, but has a more complex geological history. In Gale crater on Mars, the Curiosity rover discovered 59 igneous rocks. This article focuses on their textures (acquired from the cameras such as MAHLI and MastCam) and their geochemical compositions that have been obtained using the ChemCam instrument. Light-toned crystals have been observed in most of the rocks. They correspond to feldspars ranging from andesines/oligoclases to anorthoclases and sanidines in the leucocratic vesiculated rocks. Darker crystals observed in all igneous rocks (except the leucocratic vesiculated ones) were analyzed bymore » LIBS and mainly identified as Fe-rich pigeonites and Fe-augites. Iron oxides have been observed in all groups whereas F-bearing minerals have been detected only in few of them. From their textural analysis and their whole-rock compositions, all these 59 igneous rocks have been classified in five different groups; from primitive rocks i.e. dark aphanitic basalts/basanites, trachybasalts, tephrites and fine/coarse-grained gabbros/norites to more evolved materials i.e. porphyritic trachyandesites, leucocratic trachytes and quartz-diorites. The basalts and gabbros are found all along the traverse of the rover, whereas the felsic rocks are located before the Kimberley formation, i.e. close to the Peace Vallis alluvial fan deposits. This suggests that these alkali rocks have been transported by fluvial activity and could come from the Northern rim of the crater, and may correspond to deeper strata buried under basaltic regolith (Sautter et al., 2015). Some of the basaltic igneous rocks are surprisingly enriched in iron, presenting low Mg# similar to the nakhlite parental melt that cannot be produced by direct melting of the Dreibus and Wanke (1986) martian primitive mantle. The basaltic rocks at Gale are thus different from Gusev basalts. They could originate from different mantle reservoirs, or they could have undergone a more extensive fractional crystallization. Lastly, Gale basaltic rocks could have been the parental magma of residual liquid extending into alkali field towards trachyte composition as magma fractionated under anhydrous condition on its way to the surface before sub adiabatic ascent.« less

Experimental partitioning of Tc, Mo, Ru, and Re between solid and liquid during crystallization in Fe-Ni-S 1

NASA Astrophysics Data System (ADS)

Lazar, C.; Walker, D.; Walker, R. J.

2004-02-01

Technetium isotopes 97Tc, 98Tc and 99Tc decay to 97Mo, 98Ru and 99Ru, with half-lives of 2.6 My, 4.1 My, and 0.21 My respectively. If there were early solar system processes that resulted in significant fractionation of Tc from the daughter elements, decay of extant Tc could have led to the creation of Mo and Ru isotopic heterogeneities. To assess the potential of metallic core crystallization to fractionate these elements, we examine the partitioning behavior of Tc relative to Re, Mo and Ru in the Fe-Ni-S system between solid metal and liquid metal alloy. The experimental evidence shows that Tc behaves more like the modestly compatible siderophile element Ru than the more highly compatible siderophile element Re, and that Tc is substantially more compatible than Mo. We also demonstrate a pressure effect in the partitioning of Mo during the crystallization of Fe-Ni-S melts. For a sulfur concentration in the liquid fraction of the core of 10 wt% (16.3 at%), the Jones and Malvin (1990) parameter is -ln(1-2 × 1.09 × 0.163) ≅ 0.44, which yields: D(Re) ≅ 4.1; D(Ru) ≅ 2.3; D(Tc) ≅ 1.7; D(Mo) Lo-P ≅ 1.0;.and D(Mo) Hi-P ≅ 0.5. Our results suggest that detectable Tc-induced isotopic anomalies (≥0.1 ɛ unit) in Ru and Mo could only be produced by unrealistically extreme degrees of crystallization of metal during asteroidal core fractionation, regardless of the time scales and initial Tc abundances involved.

Rheological flow laws for multiphase magmas: An empirical approach

NASA Astrophysics Data System (ADS)

Pistone, Mattia; Cordonnier, Benoît; Ulmer, Peter; Caricchi, Luca

2016-07-01

The physical properties of magmas play a fundamental role in controlling the eruptive dynamics of volcanoes. Magmas are multiphase mixtures of crystals and gas bubbles suspended in a silicate melt and, to date, no flow laws describe their rheological behaviour. In this study we present a set of equations quantifying the flow of high-viscosity (> 105 Pa·s) silica-rich multiphase magmas, containing both crystals (24-65 vol.%) and gas bubbles (9-12 vol.%). Flow laws were obtained using deformation experiments performed at high temperature (673-1023 K) and pressure (200-250 MPa) over a range of strain-rates (5 · 10- 6 s- 1 to 4 · 10- 3 s- 1), conditions that are relevant for volcanic conduit processes of silica-rich systems ranging from crystal-rich lava domes to crystal-poor obsidian flows. We propose flow laws in which stress exponent, activation energy, and pre-exponential factor depend on a parameter that includes the volume fraction of weak phases (i.e. melt and gas bubbles) present in the magma. The bubble volume fraction has opposing effects depending on the relative crystal volume fraction: at low crystallinity bubble deformation generates gas connectivity and permeability pathways, whereas at high crystallinity bubbles do not connect and act as ;lubricant; objects during strain localisation within shear bands. We show that such difference in the evolution of texture is mainly controlled by the strain-rate (i.e. the local stress within shear bands) at which the experiments are performed, and affect the empirical parameters used for the flow laws. At low crystallinity (< 44 vol.%) we observe an increase of viscosity with increasing strain-rate, while at high crystallinity (> 44 vol.%) the viscosity decreases with increasing strain-rate. Because these behaviours are also associated with modifications of sample textures during the experiment and, thus, are not purely the result of different deformation rates, we refer to ;apparent shear-thickening; and ;apparent shear-thinning; for the behaviours observed at low and high crystallinity, respectively. At low crystallinity, increasing deformation rate favours the transfer of gas bubbles in regions of high strain localisation, which, in turn, leads to outgassing and the observed increase of viscosity with increasing strain-rate. At high crystallinity gas bubbles remain trapped within crystals and no outgassing occurs, leading to strain localisation in melt-rich shear bands and to a decrease of viscosity with increasing strain-rate, behaviour observed also in crystal-bearing suspensions. Increasing the volume fraction of weak phases induces limited variation of the stress exponent and pre-exponential factor in both apparent shear-thickening and apparent shear-thinning regimes; conversely, the activation energy is strongly dependent on gas bubble and melt volume fractions. A transient rheology from apparent shear-thickening to apparent shear-thinning behaviour is observed for a crystallinity of 44 vol.%. The proposed equations can be implemented in numerical models dealing with the flow of crystal- and bubble-bearing magmas. We present results of analytical simulations showing the effect of the rheology of three-phase magmas on conduit flow dynamics, and show that limited bubble volumes (< 10 vol.%) lead to strain localisation at the conduit margins during the ascent of crystal-rich lava domes and crystal-poor obsidian flows.

Glass transition and crystallization kinetics of a barium borosilicate glass by a non-isothermal method

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

Lopes, Andreia A. S.; Soares, Roque S.; Lima, Maria M. A.

2014-01-28

The glass transition and crystallization kinetics of a glass with a molar composition 60BaO-30B{sub 2}O{sub 3}-10SiO{sub 2} were investigated by differential scanning calorimetry (DSC) under non-isothermal conditions. DSC curves exhibited an endothermic peak associated with the glass transition and two partially overlapped exothermic peaks associated with the crystallization of the glass. The dependence of the glass transition temperature (T{sub g}) and of the maximum crystallization temperature (T{sub p}) on the heating rate was used to determine the activation energy associated with the glass transition (E{sub g}), the activation energy for crystallization (E{sub c}), and the Avrami exponent (n). X-ray diffractionmore » (XRD) revealed that barium borate (β-BaB{sub 2}O{sub 4}) was the first crystalline phase to be formed followed by the formation of barium silicate (Ba{sub 5}Si{sub 8}O{sub 21}). The variations of activation energy for crystallization and of Avrami exponent with the fraction of crystallization (χ) were also examined. When the crystallization fraction (χ) increased from 0.1 to 0.9, the value of local activation energy (E{sub c}(χ)) decreased from 554 to 458 kJ/mol for the first exothermic peak and from 1104 to 831 kJ/mol for the second exothermic peak. The value determined for the Avrami exponent was near 2 indicating a similar one-dimensional crystallization mechanism for both crystalline phases. This was confirmed by the morphological studies performed by scanning electron microscopy (SEM) on glass samples heat-treated at the first and at the second crystallization temperatures.« less

The Effects of Impurities on Protein Crystal Growth and Nucleation: A Preliminary Study

NASA Technical Reports Server (NTRS)

Schall, Constance A.

1998-01-01

Kubota and Mullin (1995) devised a simple model to account for the effects of impurities on crystal growth of small inorganic and organic molecules in aqueous solutions. Experimentally, the relative step velocity and crystal growth of these molecules asymptotically approach zero or non-zero values with increasing concentrations of impurities. Alternatively, the step velocity and crystal growth can linearly approach zero as the impurity concentration increases. The Kubota-Mullin model assumes that the impurity exhibits Langmuirian adsorption onto the crystal surface. Decreases in step velocities and subsequent growth rates are related to the fractional coverage (theta) of the crystal surface by adsorbed impurities; theta = Kx / (I +Kx), x = mole fraction of impurity in solution. In the presence of impurities, the relative step velocity, V/Vo, and the relative growth rate of a crystal face, G/Go, are proposed to conform to the following equations: V/Vo approx. = G/Go = 1 - (alpha)(theta). The adsorption of impurity is assumed to be rapid and in quasi-equilibrium with the crystal surface sites available. When the value of alpha, an effectiveness factor, is one the growth will asymptotically approach zero with increasing concentrations of impurity. At values less than one, growth approaches a non-zero value asymptotically. When alpha is much greater than one, there will be a linear relationship between impurity concentration and growth rates. Kubota and Mullin expect alpha to decrease with increasing supersaturation and shrinking size of a two dimensional nucleus. It is expected that impurity effects on protein crystal growth will exhibit behavior similar to that of impurities in small molecule growth. A number of proteins were added to purified chicken egg white lysozyme, the effect on crystal nucleation and growth assessed.

Liquid fractionation. Part I: Basic principles and experimental simulations

NASA Astrophysics Data System (ADS)

McBirney, Alexander R.; Baker, Brian H.; Nilson, Robert H.

1985-03-01

A possible explanation for the closely associated magmas of contrasting compositions erupted from many mature volcanic centers can be found in the large differences of density produced by relatively small compositional variations in liquids that evolve by crystallization or melting at the walls of shallow magma chambers. A mechanism of liquid fractionation in which differentiated liquids segragate gravitationally to form compositionally graded columns of magma may surmount the long-standing problem of explaining large volumes of highly evolved liquids that reach advanced degrees of differentiation in times that are too short to be consistent with conventional models of crystal fractionation based on crystal settling. In those types of magmas that decrease in density as they differentiate, a fractionated liquid next to a wall may form a buoyant compositional boundary layer that flows up the wall and accumulates as a separate zone in the upper levels of the reservoir. Magmas that increase in density as they differentiate will have the opposite behavior; they descend along the wall and pond on the floor. Both types of systems can be modeled using simple aqueous solutions and techniques similar to those developed by Chen and Turner (1980). The insights gained through experiments of this kind suggest a number of processes that may be responsible for common types of volcanic behavior and patterns of differentiation in shallow plutons.

The Halite-Bearing Zag and Monahans (1998) Meteorite Breccias: Shock Metamorphism, Thermal Metamorphism and Aqueous Alteration on the H-Chondrite Parent Body

NASA Technical Reports Server (NTRS)

Rubin, Alan E.; Zolensky, Michael E.; Bodnar, Robert J.

2002-01-01

Zag and Monahans (1998) are H-chondrite regolith breccias comprised mainly of lightcolored metamorphosed clasts, dark clasts that exhibit extensive silicate darkening, and a halite-bearing clastic matrix. These meteorites reflect a complex set of modification processes that occurred on the H-chondrite parent body. The light-colored clasts are thermally metamorphosed H5 and H6 rocks that were fragmented and deposited in the regolith. The dark clasts formed from light-colored clasts during shock events that melted and mobilized a significant fraction of their metallic Fe-Ni and troilite grains. The clastic matrices of these meteorites are rich in solar-wind gases. Parent-body water was required to cause leaching of chondri tic minerals and chondrule glass; the fluids became enriched in Na, K, CI, Br, AI, Ca, Mg and Fe. Evaporation of the fluids caused them to become brines as halides and alkalies became supersaturated; grains of halite (and, in the case of Monahans (1998), halite with sylvite inclusions) precipitated at low temperatures (less than or equal to 100 C) in the porous regolith. In both meteorites fluid inclusions were trapped inside the halite crystals. Primary fluid inclusions were trapped in the growing crystals; secondary inclusions formed subsequently from fluid trapped within healed fractures.

Lithium niobate single-crystal and photo-functional device

DOEpatents

Gopalan, Venkatraman; Mitchell, Terrence E.; Kitamura, Kenji; Furukawa, Yasunori

2001-01-01

Provided are lithium niobate single-crystal that requires a low voltage of not larger than 10 kV/nm for its ferroelectric polarization inversion and of which the polarization can be periodically inverted with accuracy even at such a low voltage, and a photo-functional device comprising the crystal. The crystal has a molar fraction of Li.sub.2 O/(Nb.sub.2 O.sub.5 +Li.sub.2 O) of falling between 0.49 and 0.52. The photo-functional device can convert a laser ray being incident thereon.

Space-time crystals of trapped ions.

PubMed

Li, Tongcang; Gong, Zhe-Xuan; Yin, Zhang-Qi; Quan, H T; Yin, Xiaobo; Zhang, Peng; Duan, L-M; Zhang, Xiang

2012-10-19

Spontaneous symmetry breaking can lead to the formation of time crystals, as well as spatial crystals. Here we propose a space-time crystal of trapped ions and a method to realize it experimentally by confining ions in a ring-shaped trapping potential with a static magnetic field. The ions spontaneously form a spatial ring crystal due to Coulomb repulsion. This ion crystal can rotate persistently at the lowest quantum energy state in magnetic fields with fractional fluxes. The persistent rotation of trapped ions produces the temporal order, leading to the formation of a space-time crystal. We show that these space-time crystals are robust for direct experimental observation. We also study the effects of finite temperatures on the persistent rotation. The proposed space-time crystals of trapped ions provide a new dimension for exploring many-body physics and emerging properties of matter.

The crystallization behavior and kinetics of a barium fluorozirconate type glass

NASA Technical Reports Server (NTRS)

Neilson, G. F.; Smith, G. L.; Weinberg, M. C.

1984-01-01

An investigation of the crystallization behavior of a Zr-Ba-La-Al-F glass which is subjected to isothermal heat treatments is presented. The number and nature of the crystalline phases which form and their nucleation sites are determined at three temperatures. Also, the growth rate and volume fraction of crystals which nucleate internally in the glass, when heated at 320 C, are determined as a function of time.

Progress Towards a Thermo-Mechanical Magma Chamber Forward Model for Eruption Cycles, Applied to the Columbia River Flood Basalts

NASA Astrophysics Data System (ADS)

Karlstrom, L.; Ozimek, C.

2016-12-01

Magma chamber modeling has advanced to the stage where it is now possible to develop self-consistent, predictive models that consider mechanical, thermal, and compositional magma time evolution through multiple eruptive cycles. We have developed such a thermo-mechanical-chemical model for a laterally extensive sill-like chamber beneath free surface, to understand physical controls on eruptive products through time at long-lived magmatic centers. This model predicts the relative importance of recharge, eruption, assimilation and fractional crystallization (REAFC, Lee et al., 2013) on evolving chemical composition as a function of mechanical magma chamber stability regimes. We solve for the time evolution of chamber pressure, temperature, gas volume fraction, volume, elemental concentration in the melt and crustal temperature field that accounts for moving boundary conditions associated with chamber inflation (and the possibility of coupled chambers at different depths). The density, volume fractions of melt and crystals, crustal assimilation and the changing viscosity and crustal properties of the wall rock are also tracked, along with joint solubility of water and CO2. The eventual goal is to develop an efficient forward model to invert for eruptive records at long-lived eruptive centers, where multiple types of data for eruptions are available. As a first step, we apply this model to a new compilation of eruptive data from the Columbia River Flood Basalts (CRFB), which erupted 210,000 km3 from feeder dikes in Washington, Oregon and Idaho between 16.9-6Ma. Data include volumes, timing and geochemical composition of eruptive units, along with seismic surveys and clinopyroxene geobarometry that constrain depth of storage through time. We are in the process of performing a suite of simulations varying model input parameters such as mantle melt rate, emplacement depth, wall rock compositions and rheology, and volatile content to explain volume, eruption timescales, and chemical trace aspects of CRFB eruptions. We are particularly interested in whether the large volume eruptions of the main phase Grande Ronde basalts were made possible due to the development of shallow crustal storage.

Effect of amino acids on the precipitation kinetics and Ca isotopic composition of gypsum

NASA Astrophysics Data System (ADS)

Harouaka, Khadouja; Kubicki, James D.; Fantle, Matthew S.

2017-12-01

Stirred gypsum (CaSO4 · 2H2O) precipitation experiments (initial Ωgypsum = 2.4 ± 0.14, duration ≈ 1.0-1.5 h) were conducted in the presence of the amino acids glycine (190 μM), L-alanine (190 μM), D- and L-arginine (45 μM), and L-tyrosine (200 μM) to investigate the effect of simple organic compounds on both the precipitation kinetics and Ca isotopic composition of gypsum. Relative to abiotic controls, glycine, tyrosine, and alanine inhibited precipitation rates by ∼22%, 27%, and 29%, respectively, while L- and D-arginine accelerated crystal growth by ∼8% and 48%, respectively. With the exception of tyrosine, amino acid induced inhibition resulted in fractionation factors (αs-f) associated with precipitation that were no more than 0.3‰ lower than amino acid-free controls. In contrast, the tyrosine and D- and L-arginine experiments had αs-f values associated with precipitation that were similar to the controls. Our experimental results indicate that Ca isotopic fractionation associated with gypsum precipitation is impacted by growth inhibition in the presence of amino acids. Specifically, we propose that the surface-specific binding of amino acids to gypsum can change the equilibrium fractionation factor of the bulk mineral. We investigate the hypothesis that amino acids can influence the growth of gypsum at specific crystal faces via adsorption and that different faces have distinct fractionation factors (αface-fluid). Accordingly, preferential sorption of amino acids at particular faces changes the relative, face-specific mass fluxes of Ca during growth, which influences the bulk isotopic composition of the mineral. Density functional theory (DFT) calculations suggest that the energetic favorability of glycine sorption onto gypsum crystal faces occurs in the order: (1 1 0) > (0 1 0) > (1 2 0) > (0 1 1), while glycine sorption onto the (-1 1 1) face was found to be energetically unfavorable. Face-specific fractionation factors constrained by frequency calculations of clusters derived from DFT structures vary by as much as 1.4‰. This suggests that the equilibrium fractionation factor for the bulk crystal can vary substantially, and that surface sorption can induce changes in αeq associated with gypsum precipitation. While we do not rule out the influence of kinetic isotope effects, our results clearly demonstrate that the mode of crystal growth can have a sizeable effect on the bulk fractionation factor (αs-f). Ultimately, our results suggest that the same mechanism by which organic molecules affect the morphology of a mineral can also impact the isotopic composition of the mineral. The results of our study provide valuable insight into the mechanism of Ca isotopic fractionation during gypsum precipitation. Our results are also important for establishing a framework for accurate interpretations of mineral-hosted Ca isotope records of the past, as we demonstrate a mechanistic pathway by which the biological and chemical environment can impact Ca isotopic fractionation during mineral precipitation.

Single-crystal 40Ar/39Ar incremental heating reveals bimodal sanidine ages in the Bishop Tuff

NASA Astrophysics Data System (ADS)

Andersen, N. L.; Jicha, B. R.; Singer, B. S.

2015-12-01

The 650 km3 Bishop Tuff (BT) is among the most studied volcanic deposits because it is an extensive marker bed deposited just after the Matuyama-Brunhes boundary. Reconstructions of the vast BT magma reservoir from which high-silica rhyolite erupted have long influenced thinking about how large silicic magma systems are assembled, crystallized, and mixed. Yet, the longevity of the high silica rhyolitic melt and exact timing of the eruption remain controversial due to recent conflicting 40Ar/39Ar sanidine vs. SIMS and ID-TIMS U-Pb zircon dates. We have undertaken 21 40Ar/39Ar incremental heating ages on 2 mm BT sanidine crystals from pumice in 3 widely separated outcrops of early-erupted fall and flow units. Plateau ages yield a bimodal distribution: a younger group has a mean of 766 ka and an older group gives a range between 772 and 782 ka. The younger population is concordant with the youngest ID-TIMS and SIMS U-Pb zircon ages recently published, as well as the astronomical age of BT in marine sediment. Of 21 crystals, 17 yield older, non-plateau, steps likely affected by excess Ar that would bias traditional 40Ar/39Ar total crystal fusion ages. The small spread in older sanidine ages, together with 25+ kyr of pre-eruptive zircon growth, suggest that the older sanidines are not partially outgassed xenocrysts. A bimodal 40Ar/39Ar age distribution implies that some fraction of rhyolitic melt cooled below the Ar closure temperature at least 10 ky prior to eruption. We propose that rapid "thawing" of a crystalline mush layer released older crystals into rhyolitic melt from which sanidine also nucleated and grew immediately prior to the eruption. High precision 40Ar/39Ar dating can thus provide essential information on thermo-physical processes at the millenial time scale that are critical to interpreting U-Pb zircon age distributions that are complicated by large uncertainties associated with zircon-melt U-Th systematics.

Ore-forming adakitic porphyry produced by fractional crystallization of oxidized basaltic magmas in a subcrustal chamber (Jiamate, East Junggar, NW China)

NASA Astrophysics Data System (ADS)

Hong, Tao; Xu, Xing-Wang; Gao, Jun; Peters, Stephen G.; Zhang, Di; Jielili, Reyaniguli; Xiang, Peng; Li, Hao; Wu, Chu; You, Jun; Liu, Jie; Ke, Qiang

2018-01-01

Adakitic intrusions are supposed to have a close genetic and spatial relationship to porphyry Cu deposits. However, the genesis of adakitic intrusions is still under dispute. Here, we describe newly discovered intrusive complex rocks, which are composed of ore-bearing, layered magnetite-bearing gabbroic and adakitic rocks in Jiamate, East Junggar, NW China. These Jiamate Complex intrusions have diagnostic petrologic, geochronologic and geochemical signatures that indicate they were all generated from the same oxidized precursor magma source. Additionally, these layered rocks underwent the same fractional crystallization process as the ore-bearing adakitic rocks in the adjacent Kalaxiangar Porphyry Cu Belt (KPCB) in an oceanic island arc (OIA) setting. The rocks studied for this paper include layered magnetite-bearing gabbroic intrusive rocks that contain: (1) gradual contact changes between lithological units of mafic and intermediate rocks, (2) geochemical signatures that are the same as those found in oceanic island arc (OIA) rocks, (3) typical adakitic geochemistry, and (4) similar characteristics and apparent fractional crystallization relationships of ultra-basic to basic rocks to those in the nearby Beitashan Formation and to ore-bearing adakitic rocks in the KPCB. They also display similar zircon U-Pb and zircon Hf model ages. The Jiamate Complex intrusions contain intergrowths of magnetite and layered gabbro, and the intermediate-acidic intrusions of the Complex display typical adakitic affinities. Moreover, in conjunction with previously published geochronological and geochemistry data of the mafic rocks in the Beitashan Formation and in the KPCB area, additional data generated for the Jiamate Complex intrusions rocks indicate that they were formed from fractional crystallization processes. The Jiamate Complex intrusions most likely were derived from a metasomatized mantle wedge that was underplated at the root of the Saur oceanic island arc (Saur OIA). The ore-bearing adakitic intrusions in the KPCB and the adakitic Jiamate Complex intrusions were both probably generated from the same basaltic parental magmas through fractional crystallization. In addition, characteristics of the layered, magnetite-bearing, oxidized, basaltic Jiamate Complex intrusive rocks indicate that they are likely to be the parental arc magmas for the nearby porphyry Cu deposits. This conclusion is based on new interpretations of the regional and local geology, on interpretation of new geochemical analysis, new stable isotope analysis, new geothermobarometry, and new zircon age dating as well as other techniques and interpretations.

Ore-forming adakitic porphyry produced by fractional crystallization of oxidized basaltic magmas in a subcrustal chamber (Jiamate, East Junggar, NW China)

USGS Publications Warehouse

Hong, Tao; Xu, Xing-Wang; Gao, Jun; Peters, Stephen; Zhang, Di; Jielili, Reyaniguli; Xiang, Peng; Li, Hao; Wu, Chu; You, Jun; Liu, Jie; Ke, Qiang

2018-01-01

Adakitic intrusions are supposed to have a close genetic and spatial relationship to porphyry Cu deposits. However, the genesis of adakitic intrusions is still under dispute. Here, we describe newly discovered intrusive complex rocks, which are composed of ore-bearing, layered magnetite-bearing gabbroic and adakitic rocks in Jiamate, East Junggar, NW China. These Jiamate Complex intrusions have diagnostic petrologic, geochronologic and geochemical signatures that indicate they were all generated from the same oxidized precursor magma source. Additionally, these layered rocks underwent the same fractional crystallization process as the ore-bearing adakitic rocks in the adjacent Kalaxiangar Porphyry Cu Belt (KPCB) in an oceanic island arc (OIA) setting. The rocks studied for this paper include layered magnetite-bearing gabbroic intrusive rocks that contain: (1) gradual contact changes between lithological units of mafic and intermediate rocks, (2) geochemical signatures that are the same as those found in oceanic island arc (OIA) rocks, (3) typical adakitic geochemistry, and (4) similar characteristics and apparent fractional crystallization relationships of ultra-basic to basic rocks to those in the nearby Beitashan Formation and to ore-bearing adakitic rocks in the KPCB. They also display similar zircon U-Pb and zircon Hf model ages.The Jiamate Complex intrusions contain intergrowths of magnetite and layered gabbro, and the intermediate-acidic intrusions of the Complex display typical adakitic affinities. Moreover, in conjunction with previously published geochronological and geochemistry data of the mafic rocks in the Beitashan Formation and in the KPCB area, additional data generated for the Jiamate Complex intrusions rocks indicate that they were formed from fractional crystallization processes. The Jiamate Complex intrusions most likely were derived from a metasomatized mantle wedge that was underplated at the root of the Saur oceanic island arc (Saur OIA). The ore-bearing adakitic intrusions in the KPCB and the adakitic Jiamate Complex intrusions were both probably generated from the same basaltic parental magmas through fractional crystallization. In addition, characteristics of the layered, magnetite-bearing, oxidized, basaltic Jiamate Complex intrusive rocks indicate that they are likely to be the parental arc magmas for the nearby porphyry Cu deposits. This conclusion is based on new interpretations of the regional and local geology, on interpretation of new geochemical analysis, new stable isotope analysis, new geothermobarometry, and new zircon age dating as well as other techniques and interpretations.

Generalized prolate spheroidal wave functions for optical finite fractional Fourier and linear canonical transforms.

PubMed

Pei, Soo-Chang; Ding, Jian-Jiun

2005-03-01

Prolate spheroidal wave functions (PSWFs) are known to be useful for analyzing the properties of the finite-extension Fourier transform (fi-FT). We extend the theory of PSWFs for the finite-extension fractional Fourier transform, the finite-extension linear canonical transform, and the finite-extension offset linear canonical transform. These finite transforms are more flexible than the fi-FT and can model much more generalized optical systems. We also illustrate how to use the generalized prolate spheroidal functions we derive to analyze the energy-preservation ratio, the self-imaging phenomenon, and the resonance phenomenon of the finite-sized one-stage or multiple-stage optical systems.

Rhenium-osmium concentration and isotope systematics in group IIAB iron meteorites

USGS Publications Warehouse

Morgan, J.W.; Horan, M.F.; Walker, R.J.; Grossman, J.N.

1995-01-01

Rhenium and osmium abundances, and osmium isotopic compositions were measured by negative thermal ionization mass spectrometry in thirty samples, including replicates, of five IIA and eight IIB iron meteorites. Log plots of Os vs. Re abundances for IIA and IIB irons describe straight lines that approximately converge on Lombard, which has the lowest Re and Os abundances and highest 187Re/188Os measured in a IIA iron to date. The linear IIA trend may be exactly reproduced by fractional crystallization, but is not well fitted using variable partition coefficients. The IIB iron trend, however, cannot be entirely explained by simple fractional crystallization. One explanation is that small amounts of Re and Os were added to the asteroid core during the final stages of crystallization. Another possibility is that diffusional enrichment of Os may have occurred in samples most depleted in Re and Os. -from Authors

Possible Mechanisms for Turbofan Engine Ice Crystal Icing at High Altitude

NASA Technical Reports Server (NTRS)

Tsao, Jen-Ching; Struk, Peter M.; Oliver, Michael

2014-01-01

A thermodynamic model is presented to describe possible mechanisms of ice formation on unheated surfaces inside a turbofan engine compression system from fully glaciated ice crystal clouds often formed at high altitude near deep convective weather systems. It is shown from the analysis that generally there could be two distinct types of ice formation: (1) when the "surface freezing fraction" is in the range of 0 to 1, dominated by the freezing of water melt from fully or partially melted ice crystals, the ice structure is formed from accretion with strong adhesion to the surface, and (2) when the "surface melting fraction" is the range of 0 to 1, dominated by the further melting of ice crystals, the ice structure is formed from accumulation of un-melted ice crystals with relatively weak bonding to the surface. The model captures important qualitative trends of the fundamental ice-crystal icing phenomenon reported earlier1,2 from the research collaboration work by NASA and the National Research Council (NRC) of Canada. Further, preliminary analysis of test data from the 2013 full scale turbofan engine ice crystal icing test3 conducted in the NASA Glenn Propulsion Systems Laboratory (PSL) has also suggested that (1) both types of ice formation occurred during the test, and (2) the model has captured some important qualitative trend of turning on (or off) the ice crystal ice formation process in the tested engine low pressure compressor (LPC) targeted area under different icing conditions that ultimately would lead to (or suppress) an engine core roll back (RB) event.

Possible Mechanisms for Turbofan Engine Ice Crystal Icing at High Altitude

NASA Technical Reports Server (NTRS)

Tsao, Jen-Ching; Struk, Peter M.; Oliver, Michael J.

2016-01-01

A thermodynamic model is presented to describe possible mechanisms of ice formation on unheated surfaces inside a turbofan engine compression system from fully glaciated ice crystal clouds often formed at high altitude near deep convective weather systems. It is shown from the analysis that generally there could be two distinct types of ice formation: (1) when the "surface freezing fraction" is in the range of 0 to 1, dominated by the freezing of water melt from fully or partially melted ice crystals, the ice structure is formed from accretion with strong adhesion to the surface, and (2) when the "surface melting fraction" is the range of 0 to 1, dominated by the further melting of ice crystals, the ice structure is formed from accumulation of un-melted ice crystals with relatively weak bonding to the surface. The model captures important qualitative trends of the fundamental ice-crystal icing phenomenon reported earlier (Refs. 1 and 2) from the research collaboration work by NASA and the National Research Council (NRC) of Canada. Further, preliminary analysis of test data from the 2013 full scale turbofan engine ice crystal icing test (Ref. 3) conducted in the NASA Glenn Propulsion Systems Laboratory (PSL) has also suggested that (1) both types of ice formation occurred during the test, and (2) the model has captured some important qualitative trend of turning on (or off) the ice crystal ice formation process in the tested engine low pressure compressor (LPC) targeted area under different icing conditions that ultimately would lead to (or suppress) an engine core roll back (RB) event.

The assessment of pore connectivity in hierarchical zeolites using positron annihilation lifetime spectroscopy: instrumental and morphological aspects.

PubMed

Zubiaga, Asier; Warringham, Robbie; Boltz, Marilyne; Cooke, David; Crivelli, Paolo; Gidley, David; Pérez-Ramírez, Javier; Mitchell, Sharon

2016-04-07

Recent studies demonstrated the power of positron annihilation lifetime spectroscopy (PALS) to characterise the connectivity and corresponding effectiveness of hierarchical pore networks in zeolites. This was based on the fractional escape of ortho-positronium (Ps), formed within the micropore framework, to vacuum. To further develop this technique, here we assess the impact of the positron implantation energy and of the zeolite crystal size and the particle morphology. Conventional measurements using fast positrons and beam measurements applying moderated positrons both readily distinguish purely microporous ZSM-5 zeolites comprised of single crystals or crystal aggregates. Unlike beam measurements, however, conventional measurements fail to discriminate model hierarchical zeolites with open or constricted mesopore architectures. Several steps are taken to rationalise these observations. The dominant contribution of Ps diffusion to the PALS response is confirmed by capping the external surface of the zeolite crystals with tetraethylorthosilicate, which greatly enhances the sensitivity to the micropore network. A one-dimensional model is constructed to predict the out-diffusion of Ps from a zeolite crystal, which is validated experimentally by comparing coffin-shaped single crystals of varying size. Calculation of the trends expected on the application of fast or moderated positrons indicates that the distinctions in the initial distribution of Ps at the crystal level cannot explain the limited sensitivity of the former to the mesopore architecture. Instead, we propose that the greater penetration of fast positrons within the sample increases the probability of Ps re-entry from intercrystalline voids into mesopores connected with the external surface of zeolite crystals, thereby reducing their fractional escape.

Phenomenological model of spin crossover in molecular crystals as derived from atom-atom potentials.

PubMed

Sinitskiy, Anton V; Tchougréeff, Andrei L; Dronskowski, Richard

2011-08-07

The method of atom-atom potentials, previously applied to the analysis of pure molecular crystals formed by either low-spin (LS) or high-spin (HS) forms (spin isomers) of Fe(II) coordination compounds (Sinitskiy et al., Phys. Chem. Chem. Phys., 2009, 11, 10983), is used to estimate the lattice enthalpies of mixed crystals containing different fractions of the spin isomers. The crystals under study were formed by LS and HS isomers of Fe(phen)(2)(NCS)(2) (phen = 1,10-phenanthroline), Fe(btz)(2)(NCS)(2) (btz = 5,5',6,6'-tetrahydro-4H,4'H-2,2'-bi-1,3-thiazine), and Fe(bpz)(2)(bipy) (bpz = dihydrobis(1-pyrazolil)borate, and bipy = 2,2'-bipyridine). For the first time the phenomenological parameters Γ pertinent to the Slichter-Drickamer model (SDM) of several materials were independently derived from the microscopic model of the crystals with use of atom-atom potentials of intermolecular interaction. The accuracy of the SDM was checked against the numerical data on the enthalpies of mixed crystals. Fair semiquantitative agreement with the experimental dependence of the HS fraction on temperature was achieved with use of these values. Prediction of trends in Γ values as a function of chemical composition and geometry of the crystals is possible with the proposed approach, which opens a way to rational design of spin crossover materials with desired properties. This journal is © the Owner Societies 2011

Calculating the permeability coefficients of mixed matrix membranes of polydimethylsiloxane and silicalite crystals to various ethanol-water solutions using molecular simulations.

EPA Science Inventory

The permeability coefficients of mixed matrix membranes of polydimethylsiloxane (PDMS) and silicalite crystal are taken as the sum of the permeability coefficients of membrane components each weighted by their associated mass fraction. The permeability coefficient of a membrane c...

An Extensive Analysis of Preservice Elementary Teachers' Knowledge of Fractions

ERIC Educational Resources Information Center

Newton, Kristie Jones

2008-01-01

The study of preservice elementary teachers' knowledge of fractions is important because fractions are notoriously difficult to learn and teach. Unfortunately, studies of preservice teachers' fraction knowledge are limited and have focused primarily on division. The present study included all four operations to provide a more comprehensive…

Process of electrolysis and fractional crystallization for aluminum purification

DOEpatents

Dawless, R.K.; Bowman, K.A.; Mazgaj, R.M.; Cochran, C.N.

1983-10-25

A method is described for purifying aluminum that contains impurities, the method including the step of introducing such aluminum containing impurities to a charging and melting chamber located in an electrolytic cell of the type having a porous diaphragm permeable by the electrolyte of the cell and impermeable to molten aluminum. The method includes further the steps of supplying impure aluminum from the chamber to the anode area of the cell and electrolytically transferring aluminum from the anode area to the cathode through the diaphragm while leaving impurities in the anode area, thereby purifying the aluminum introduced into the chamber. The method includes the further steps of collecting the purified aluminum at the cathode, and lowering the level of impurities concentrated in the anode area by subjecting molten aluminum and impurities in said chamber to a fractional crystallization treatment wherein eutectic-type impurities crystallize and precipitate out of the aluminum. The eutectic impurities that have crystallized are physically removed from the chamber. The aluminum in the chamber is now suited for further purification as provided in the above step of electrolytically transferring aluminum through the diaphragm. 2 figs.

Process of electrolysis and fractional crystallization for aluminum purification

DOEpatents

Dawless, Robert K.; Bowman, Kenneth A.; Mazgaj, Robert M.; Cochran, C. Norman

1983-10-25

A method for purifying aluminum that contains impurities, the method including the step of introducing such aluminum containing impurities to a charging and melting chamber located in an electrolytic cell of the type having a porous diaphragm permeable by the electrolyte of the cell and impermeable to molten aluminum. The method includes further the steps of supplying impure aluminum from the chamber to the anode area of the cell and electrolytically transferring aluminum from the anode area to the cathode through the diaphragm while leaving impurities in the anode area, thereby purifying the aluminum introduced into the chamber. The method includes the further steps of collecting the purified aluminum at the cathode, and lowering the level of impurities concentrated in the anode area by subjecting molten aluminum and impurities in said chamber to a fractional crystallization treatment wherein eutectic-type impurities crystallize and precipitate out of the aluminum. The eutectic impurities that have crystallized are physically removed from the chamber. The aluminum in the chamber is now suited for further purification as provided in the above step of electrolytically transferring aluminum through the diaphragm.

Effects of polymer type and storage relative humidity on the kinetics of felodipine crystallization from amorphous solid dispersions.

PubMed

Rumondor, Alfred C F; Stanford, Lindsay A; Taylor, Lynne S

2009-12-01

The objective of this study was to investigate the effects of polymer type and storage relative humidity (RH) on the crystallization kinetics of felodipine from amorphous solid dispersions. Crystallization of the model drug felodipine from amorphous solid dispersion samples containing poly(vinyl pyrrolidone) (PVP) and hypromellose acetate succinate (HPMCAS) were evaluated. Samples at three different drug-polymer weight ratios (10, 25, and 50 wt. % polymer) were prepared and stored at six different RHs (0%, 32%, 52% or 66%, 75%, 86%, and 93%). Periodically, the fraction of the drug that had crystallized from the samples was quantified using powder X-ray diffractometry (PXRD). Felodipine crystallization rates from PVP-containing dispersions were found to be very sensitive to changes in storage RH, while crystallization rates from HPMCAS-containing dispersions were not. PVP and HPMCAS were similar in terms of their ability to inhibit crystallization at low RH, but when the storage RH was increased to 75% or above, felodipine crystallization from PVP-containing solid dispersions proceeded much faster. It is hypothesized that this trend was caused by moisture-induced drug-polymer immiscibility in PVP-felodipine system. For PVP-containing solid dispersion samples stored at 75% RH and above, crystallization of the model drug felodipine seemed to approach a kinetic plateau, whereby a fraction of the drug still remained amorphous even after storage for 500 days or more. The physical stability of solid dispersions as a function of RH is highly dependent on the polymer used to form the solid dispersion, with PVP-containing dispersions being much less physically stable at high RH than HPMCAS-containing dispersions.

No effect of H2O degassing on the oxidation state of magmatic liquids

NASA Astrophysics Data System (ADS)

Waters, Laura E.; Lange, Rebecca A.

2016-08-01

The underlying cause for why subduction-zone magmas are systematically more oxidized than those formed at mid-ocean spreading ridges is a topic of vigorous debate. It is either a primary feature inherited from the subduction of oxidized oceanic crust into the mantle or a secondary feature that develops because of H2O degassing and/or magma differentiation. Low total iron contents and high melt H2O contents render rhyolites sensitive to any effect of H2O degassing on ferric-ferrous ratios. Here, pre-eruptive magmatic Fe2+ concentrations, measured using Fe-Ti oxides that co-crystallized with silicate phenocrysts under hydrous conditions, are compared with Fe2+ post-eruptive concentrations in ten crystal-poor, fully-degassed obsidian samples; five are microlite free. No effect of H2O degassing on the ferric-ferrous ratio is found. In addition, Fe-Ti oxide data from this study and the literature show that arc magmas are systematically more oxidized than both basalts and hydrous silicic melts from Iceland and Yellowstone prior to extensive degassing. Nor is there any evidence that differentiation (i.e., crystal fractionation, crustal assimilation) is the cause of the higher redox state of arc magmas relative to those of Iceland/Yellowstone rhyolites. Instead, the evidence points to subduction of oxidized crust and the release of an H2O-rich fluid and/or melt with a high oxygen fugacity (fO2), which plays a role during H2O-flux melting of the mantle in creating basalts that are relatively oxidized.

Designed Single-Step Synthesis, Structure, and Derivative Textural Properties of Well-Ordered Layered Penta-Coordinate Silicon Alcoholate Complexes

PubMed Central

Li, Xiansen; Michaelis, Vladimir K.; Ong, Ta-Chung; Smith, Stacey J.; Griffin, Robert G.; Wang, Evelyn N.

2014-01-01

The controllable synthesis of well-ordered layered materials with specific nanoarchitecture poses a grand challenge in materials chemistry. We report the solvothermal synthesis of two structurally analogous 5-coordinate organosilicate complexes via a novel transesterification mechanism. Since the polycrystalline nature of the intrinsic hypervalent Si complex thwarts the endeavor in determining its structure, a novel strategy concerning the elegant addition of a small fraction of B species as an effective crystal growth mediator and a sacrificial agent is proposed to directly prepare diffraction-quality single crystals without disrupting the intrinsic elemental type. In the determined crystal structure, two monomeric primary building units (PBUs) self-assemble into a dimeric asymmetric secondary BU via strong Na+-O2− ionic bonds. The designed one-pot synthesis is straightforward, robust, and efficient, leading to a well-ordered (10ī)-parallel layered Si complex with its principal interlayers intercalated with extensive van der Waals gaps in spite of the presence of substantial Na+ counterions as a result of unique atomic arrangement in its structure. On the other hand, upon fast pyrolysis, followed by acid leaching, both complexes are converted into two SiO2 composites bearing BET surface areas of 163.3 and 254.7 m2 g−1 for the pyrolyzed intrinsic and B-assisted Si complexes, respectively. The transesterification methodology merely involving alcoholysis but without any hydrolysis side reaction is designed to have generalized applicability for use in synthesizing new layered metal-organic compounds with tailored PBUs and corresponding metal oxide particles with hierarchical porosity. PMID:24737615

Equilibrium carbon and hydrogen isotope fractionation in iron

NASA Astrophysics Data System (ADS)

Schauble, E. A.

2009-12-01

Recent theoretical and experimental studies (e.g., [1-3]) have suggested that Si- and Fe-isotopic signatures can be used to characterize the compositions and conditions of segregation of metallic cores in planetary interiors. This study expands the theoretical framework to include carbon and hydrogen, which may also be alloying elements. Hydrogen (D/H) and carbon (13C/12C) fractionations in iron-rich metallic melts are estimated by modeling analogous iron-rich crystals, i.e., dhcp-FeH and η-Fe2C. C- and H-atoms in these crystals are completely coordinated by iron. The driving energy for equilibrium fractionation is assumed to come from the reduction of vibrational frequencies when heavy isotopes are substituted for light ones; vibrations are assumed to be harmonic. This treatment is crude at high temperature, and for the relatively anharmonic vibrations typical of hydrogen-bearing substances, but may provide a reasonably accurate, semi-quantitative approximation of real fractionation behavior. Vibrational frequencies of all crystals are modeled with density functional theory, using gradient-corrected functionals and ultrasoft pseudopotentials. For both carbon and hydrogen, the models suggest that the metal phase will be strongly depleted in heavy isotopes. At 2000 K, 1 atm, η-Fe2C will have 3‰ lower 13C/12C than coexisting diamond. Combining this result with previous high-temperature theoretical and experimental studies (e.g., [4]), metal-graphite fractionation is expected to be very similar, while metal-CO2 fractionation will be almost twice as large, ca. -5‰. Deuterium/hydrogen fractionations are expected to be an order of magnitude larger, with 50-70‰ lower D/H in dhcp-FeH than in coexisting H2 gas at 2000 K, and approximately 100‰ lower D/H than water vapor. These fractionations are much larger than those inferred for silicon and iron, as expected given the differences in atomic mass. References: 1. Georg et al. (2007) Nature 447:1102; 2. Rustad & Yin (2009) Nature Geoscience doi:10.1038/ngeo546; 3. Polyakov (2009) Science 323:912; 4. Polyakov & Kharlashina (1995) GCA 59:2561.

Competition of the connectivity with the local and the global order in polymer melts and crystals

NASA Astrophysics Data System (ADS)

Bernini, S.; Puosi, F.; Barucco, M.; Leporini, D.

2013-11-01

The competition between the connectivity and the local or global order in model fully flexible chain molecules is investigated by molecular-dynamics simulations. States with both missing (melts) and high (crystal) global order are considered. Local order is characterized within the first coordination shell (FCS) of a tagged monomer and found to be lower than in atomic systems in both melt and crystal. The role played by the bonds linking the tagged monomer to FCS monomers (radial bonds), and the bonds linking two FCS monomers (shell bonds) is investigated. The detailed analysis in terms of Steinhardt's orientation order parameters Ql (l = 2 - 10) reveals that increasing the number of shell bonds decreases the FCS order in both melt and crystal. Differently, the FCS arrangements organize the radial bonds. Even if the molecular chains are fully flexible, the distribution of the angle formed by adjacent radial bonds exhibits sharp contributions at the characteristic angles θ ≈ 70°, 122°, 180°. The fractions of adjacent radial bonds with θ ≈ 122°, 180° are enhanced by the global order of the crystal, whereas the fraction with 70° ≲ θ ≲ 110° is nearly unaffected by the crystallization. Kink defects, i.e., large lateral displacements of the chains, are evidenced in the crystalline state.

Systematic Approach to Electrostatically Induced 2D Crystallization of Nanoparticles at Liquid Interfaces

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

Fukuto, M.; Kewalramani, S.; Wang, S.

2011-02-07

We report an experimental demonstration of a strategy for inducing two-dimensional (2D) crystallization of charged nanoparticles on oppositely charged fluid interfaces. This strategy aims to maximize the interfacial adsorption of nanoparticles, and hence their lateral packing density, by utilizing a combination of weakly charged particles and a high surface charge density on the planar interface. In order to test this approach, we investigated the assembly of cowpea mosaic virus (CPMV) on positively charged lipid monolayers at the aqueous solution surface, by means of in situ X-ray scattering measurements at the liquid-vapor interface. The assembly was studied as a function ofmore » the solution pH, which was used to vary the charge on CPMV, and of the mole fraction of the cationic lipid in the binary lipid monolayer, which set the interface charge density. The 2D crystallization of CPMV occurred in a narrow pH range just above the particle's isoelectric point, where the particle charge was weakly negative, and only when the cationic-lipid fraction in the monolayer exceeded a threshold. The observed 2D crystals exhibited nearly the same packing density as the densest lattice plane within the known 3D crystals of CPMV. The above electrostatic approach of maximizing interfacial adsorption may provide an efficient route to the crystallization of nanoparticles at aqueous interfaces.« less

Volcanic-plutonic connections and metal fertility of highly evolved magma systems: A case study from the Herberton Sn-W-Mo Mineral Field, Queensland, Australia

NASA Astrophysics Data System (ADS)

Cheng, Yanbo; Spandler, Carl; Chang, Zhaoshan; Clarke, Gavin

2018-03-01

Understanding the connection between the highly evolved intrusive and extrusive systems is essential to explore the evolution of high silicic magma systems, which plays an important role in discussions of planetary differentiation, the growth of continents, crustal evolution, and the formation of highly evolved magma associated Sn-W-Mo mineral systems. To discern differences between "fertile" and "non-fertile" igneous rocks associated with Sn-W-Mo mineralization and reveal the genetic links between coeval intrusive and extrusive rocks, we integrate whole rock geochemistry, geochronology and Hf isotope signatures of igneous zircons from contemporaneous plutonic and volcanic rocks from the world-class Herberton Mineral Field of Queensland, Australia. The 310-300 Ma intrusive rocks and associated intra-plutonic W-Mo mineralization formed from relatively oxidized magmas after moderate degrees of crystal fractionation. The geochemical and isotopic features of the coeval volcanic succession are best reconciled utilizing the widely-accepted volcanic-plutonic connection model, whereby the volcanic rocks represent fractionated derivatives of the intrusive rocks. Older intrusions emplaced at 335-315 Ma formed from relatively low fO2 magmas that fractionated extensively to produce highly evolved granites that host Sn mineralization. Coeval volcanic rocks of this suite are compositionally less evolved than the intrusive rocks, thereby requiring a different model to link these plutonic-volcanic sequences. In this case, we propose that the most fractionated magmas were not lost to volcanism, but instead were effectively retained at the plutonic level, which allowed further localized build-up of volatiles and lithophile metals in the plutonic environment. This disconnection to the volcanism and degassing may be a crucial step for forming granite-hosted Sn mineralization. The transition between these two igneous regimes in Herberton region over a ∼30 m.y. period is attributed to a change from an early compressive tectonic environment with a thickened crust, to conditions of crustal thinning and lithospheric extension due to progressive slab rollback. Such tectonic transitions may provide favorable conditions for intrusion-related mineralization. Given the common occurrence of volcanic and plutonic rocks associated with Sn-W-Mo mineralization worldwide, we suggest that a combined understanding of temporal tectonic evolution and plutonic-volcanic connections can assist in assessment of regional-scale mineralization potential, which in turn can aid strategies for future ore deposit exploration.

The Effect Of Additional Detergent In Crude Palm Oil In The Process Of Separation Stearin

NASA Astrophysics Data System (ADS)

Rezekyah Hasibuan, Vina; aini, Nur; Febriyanti; Ayubi Pane, Salahudin Al

2018-03-01

This study aims to find out how much stearin is formed from the addition of detergent and to understand the process of separation of crude olein with crude stearin from raw material of crude palm oil (CPO). Using a detergent fractionation system, detergent fractionation is a continuous crystallization of oil with controlled cooling and the separation of fractions by weight or centrifuge after supplementing surfactant.

Oxygen isotopes reveal crustal contamination and a large, still partially molten magma chamber in Chaîne des Puys (French Massif Central)

NASA Astrophysics Data System (ADS)

France, Lydéric; Demacon, Mickael; Gurenko, Andrey A.; Briot, Danielle

2016-09-01

The two main magmatic properties associated with explosive eruptions are high viscosity of silica-rich magmas and/or high volatile contents. Magmatic processes responsible for the genesis of such magmas are differentiation through crystallization, and crustal contamination (or assimilation) as this process has the potential to enhance crystallization and add volatiles to the initial budget. In the Chaîne des Puy series (French Massif Central), silica- and H2O-rich magmas were only emitted during the most recent eruptions (ca. 6-15 ka). Here, we use in situ measurements of oxygen isotopes in zircons from two of the main trachytic eruptions from the Chaîne des Puys to track the crustal contamination component in a sequence that was previously presented as an archetypal fractional crystallization series. Zircons from Sarcoui volcano and Puy de Dôme display homogeneous oxygen isotope compositions with δ18O = 5.6 ± 0.25‰ and 5.6 ± 0.3‰, respectively, and have therefore crystallized from homogeneous melts with δ18Omelt = 7.1 ± 0.3‰. Compared to mantle derived melts resulting from pure fractional crystallization (δ18Odif.mant. = 6.4 ± 0.4‰), those δ18Omelt values are enriched in 18O and support a significant role of crustal contamination in the genesis of silica-rich melts in the Chaîne des Puys. Assimilation-fractional-crystallization models highlight that the degree of contamination was probably restricted to 5.5-9.5% with Rcrystallization/Rassimilation varying between 8 and 14. The very strong intra-site homogeneity of the isotopic data highlights that magmas were well homogenized before eruption, and consequently that crustal contamination was not the trigger of silica-rich eruptions in the Chaîne des Puys. The exceptionally strong inter-site homogeneity of the isotopic data brings to light that Sarcoui volcano and Puy de Dôme were fed by a single large magma chamber. Our results, together with recent thermo-kinetic models and an experimental simulation (Martel et al., 2013), support the existence of a large ( 6-15 km3), still partially molten mid-crustal reservoir (10-12 km deep) that is filled with silica-rich magma. Calculated oxygen isotope compositions of the trachytic melts that crystallized the analyzed zircons for Puy de Dôme, Sarcoui dome, and Sarcoui phreatomagmatic deposits, and the range of values for each analyzed zircon grain. The range for trachytes obtained by pure fractional crystallization of mantle melts is given for comparison. See text for details on calculations. Chemical differentiation trend of Chaîne des Puys magmas (data from Boivin et al., 2009), and results of the fractional crystallization models presented herein and in Table 3. L1 is obtained after the first step of differentiation, and L2 after the second. The composition of Sarcoui trachytes is identified by an X. S3.1. Core-rim variations for oxygen isotope compositions of the studied zircons. S3.2. Oxygen isotope compositions of the various zircon domains observed with cathodoluminescence imaging (dark versus bright), and for zircons with different types of zoning (oscillatory versus sector). No systematic variation is observed.

Melt density and the average composition of basalt

NASA Technical Reports Server (NTRS)

Stolper, E.; Walker, D.

1980-01-01

Densities of residual liquids produced by low pressure fractionation of olivine-rich melts pass through a minimum when pyroxene and plagioclase joint the crystallization sequence. The observation that erupted basalt compositions cluster around the degree of fractionation from picritic liquids corresponding to the density minimum in the liquid line of descent may thus suggest that the earth's crust imposes a density fiber on the liquids that pass through it, favoring the eruption of the light liquids at the density minimum over the eruption of denser more fractionated and less fractionated liquids.

Characteristics of a liquid-crystal-filled composite lattice terahertz bandgap fiber

NASA Astrophysics Data System (ADS)

Bai, Jinjun; Ge, Meilan; Wang, Shasha; Yang, Yanan; Li, Yong; Chang, Shengjiang

2018-07-01

A new type of terahertz fiber is presented based on composite lattice photonic crystal bandgap. The cladding is filled selectively with the nematic liquid crystal 5CB which is sensitive to the electric field. The terahertz wave can be modulated by using the electric field to control the orientation of liquid crystal molecules. The plane wave expansion method and the finite element method are employed to theoretically analyze bandgap characteristics, polarization characteristics, energy fraction and material absorption loss. The results show that this fiber structure can be used as tunable terahertz polarization controller.

Electronegativity, charge transfer, crystal field strength, and the point charge model revisited.

PubMed

Tanner, Peter A; Ning, Lixin

2013-02-21

Although the optical spectra of LnCl(6)(3-) systems are complex, only two crystal field parameters, B(40) and B(60), are required to model the J-multiplet crystal field splittings in octahedral symmetry. It is found that these parameters exhibit R(-5) and R(-7) dependence, respectively, upon the ionic radius Ln(3+)(VI), but not upon the Ln-Cl distance. More generally, the crystal field strengths of LnX(6) systems (X = Br, Cl, F, O) exhibit linear relationships with ligand electronegativity, charge transfer energy, and fractional ionic character of the Ln-X bond.

U-series disequilibria in crystals: ages as tracers

NASA Astrophysics Data System (ADS)

Cooper, K. M.

2005-12-01

U-series disequilibria offer a unique perspective on the fates of crystals within magmatic systems. In addition to delimiting the timescales of magmatic processes, crystal ages can be used as a tracer of different crystal populations even in the case where only subtle differences exist between major- and trace-element chemistries of populations. For example, 226Ra-230Th ages of crystals in Mt St Helens lavas erupted since 2 ka are in some cases several kyr older than eruption ages which, when combined with significant Ra-Th disequilibria in the whole-rocks, suggests protracted crystal storage and entrainment in subsequent batches of magma passing through the reservoir. More broadly, in many cases 230Th-238U and 226Ra-230Th ages measured in the same crystals are discordant. This pattern likely indicates progressive and/or episodic crystal growth where the Th-U ages more closely represent average crystallization ages while Ra-Th ages are weighted toward recent growth, suggesting in turn that some significant fraction of the mass of crystals represent xenocrysts or "antecrysts" recycled from earlier generations of magmas within the same system. Conversely, in cases where ages of different parent-daughter pairs are concordant, mineral separates must be dominated by crystal growth within a relatively narrow time interval relative to the half-life of the shortest-lived daughter isotope. The duration of the crystal record within a given magma can be complicated by crystal recycling and obscured by average ages derived from measurement of bulk mineral separates. One way to extract more information about the proportion and ages of older and younger parts of the crystal population(s) is to analyze different size fractions within the same sample; for example, analyses of different sizes of plagioclase from the ongoing eruption at Mt St Helens are in progress. U-series ages and other crystal-scale geochemical information can also be a powerful combination. For example, preservation of major- or trace-element disequilibrium between zones within crystals limits the duration of crystal residence at high temperature; when combined with absolute age information from U-series disequilibria, these data can provide clues about the thermal conditions of crystal storage and thus whether such storage is likely to have occurred in a mostly-liquid or mostly-crystalline part of the magma system.

LABORATORY AND FIELD EVALUATION OF CRYSTALLIZED DOW 704 OIL ON THE PERFORMANCE OF THE WINS PM2.5 FRACTIONATOR

EPA Science Inventory

Subsequent to the 1997 promulgation of the Federal Reference Method (FRM) for monitoring PM2.5 in ambient air, the United States Environmental Protection Agency (USEPA) received reports that the Dow 704 diffusion oil used in the method's WINS fractionator would occasionally cry...

Tracking magmatic processes through Zr/Hf ratios in rocks and Hf and Ti zoning in zircons: An example from the Spirit Mountain batholith, Nevada

USGS Publications Warehouse

Lowery, Claiborne L.E.; Miller, C.F.; Walker, B.A.; Wooden, J.L.; Mazdab, F.K.; Bea, F.

2006-01-01

Zirconium and Hf are nearly identical geochemically, and therefore most of the crust maintains near-chondritic Zr/Hf ratios of ???35-40. By contrast, many high-silica rhyolites and granites have anomalously low Zr/Hf (15-30). As zircon is the primary reservoir for both Zr and Hf and preferentially incorporates Zr, crystallization of zircon controls Zr/ Hf, imprinting low Zr/Hf on coexisting melt. Thus, low Zr/Hf is a unique fingerprint of effective magmatic fractionation in the crust. Age and compositional zonation in zircons themselves provide a record of the thermal and compositional histories of magmatic systems. High Hf (low Zr/ Hf) in zircon zones demonstrates growth from fractionated melt, and Ti provides an estimate of temperature of crystallization (TTiZ) (Watson and Harrison, 2005). Whole-rock Zr/Hf and zircon zonation in the Spirit Mountain batholith, Nevada, document repeated fractionation and thermal fluctuations. Ratios of Zr/Hf are ???30-40 for cumulates and 18-30 for high-SiO2 granites. In zircons, Hf (and U) are inversely correlated with Ti, and concentrations indicate large fluctuations in melt composition and TTiZ (>100??C) for individual zircons. Such variations are consistent with field relations and ion-probe zircon geochronology that indicate a >1 million year history of repeated replenishment, fractionation, and extraction of melt from crystal mush to form the low Zr/Hf high-SiO2 zone. ?? 2006 The Mineralogical Society.

Crystallization of sheared hard spheres at 64.5% volume fraction

NASA Astrophysics Data System (ADS)

Swinney, H. L.; Rietz, F.; Schroeter, M.; Radin, C.

2017-11-01

A classic experiment by G.D. Scott Nature 188, 908, 1960) showed that pouring balls into a rigid container filled the volume to an upper limit of 64% of the container volume, which is well below the 74% volume fraction filled by spheres in a hexagonal close packed (HCP) or face center cubic (FCC) lattice. Subsequent experiments have confirmed a ``random closed packed'' (RCP) fraction of about 64%. However, the physics of the RCP limit has remained a mystery. Our experiment on a cubical box filled with 49400 weakly sheared glass spheres reveals a first order phase transition from a disordered to an ordered state at a volume fraction of 64.5%. The ordered state consists of crystallites of mixed FCC and HCP symmetry that coexist with the amorphous bulk. The transition is initiated by homogeneous nucleation: in the shearing process small crystallites with about ten or fewer spheres dissolve, while larger crystallites grow. A movie illustrates the crystallization process. German Academic Exchange Service (DAAD), German Research Foundation (DFG), NSF DMS, and R.A. Welch Foundation.

Trace element evaluation of a suite of rocks from Reunion Island, Indian Ocean

USGS Publications Warehouse

Zielinski, R.A.

1975-01-01

Reunion Island consists of an olivine-basalt shield capped by a series of flows and intrusives ranging from hawaiite through trachyte. Eleven rocks representing the total compositional sequence have been analyzed for U, Th and REE. Eight of the rocks (group 1) have positive-slope, parallel, chondrite-normalized REE fractionation patterns. Using a computer model, the major element compositions of group 1 whole rocks and observed phenocrysts were used to predict the crystallization histories of increasingly residual liquids, and allowed semi-quantitative verification of origin by fractional crystallization of the olivine-basalt parent magma. Results were combined with mineral-liquid distribution coefficient data to predict trace element abundances, and existing data on Cr, Ni, Sr and Ba were also successfully incorporated in the model. The remaining three rocks (group 2) have nonuniform positive-slope REE fractionation patterns not parallel to group 1 patterns. Rare earth fractionation in a syenite is explained by partial melting of a source rich in clinopyroxene and/or hornblende. The other two rocks of group 2 are explained as hybrids resulting from mixing of syenite and magmas of group 1. ?? 1975.

Solving Fuzzy Fractional Differential Equations Using Zadeh's Extension Principle

PubMed Central

Ahmad, M. Z.; Hasan, M. K.; Abbasbandy, S.

2013-01-01

We study a fuzzy fractional differential equation (FFDE) and present its solution using Zadeh's extension principle. The proposed study extends the case of fuzzy differential equations of integer order. We also propose a numerical method to approximate the solution of FFDEs. To solve nonlinear problems, the proposed numerical method is then incorporated into an unconstrained optimisation technique. Several numerical examples are provided. PMID:24082853

Compositional and microstructural design of highly bioactive P2O5-Na2O-CaO-SiO2 glass-ceramics.

PubMed

Peitl, Oscar; Zanotto, Edgar D; Serbena, Francisco C; Hench, Larry L

2012-01-01

Bioactive glasses having chemical compositions between 1Na(2)O-2CaO-3SiO(2) (1N2C3S) and 1.5Na(2)O-1.5CaO-3SiO(2) (1N1C2S) containing 0, 4 and 6 wt.% P(2)O(5) were crystallized through two stage thermal treatments. By carefully controlling these treatments we separately studied the effects on the mechanical properties of two important microstructural features not studied before, crystallized volume fraction and crystal size. Fracture strength, elastic modulus and indentation fracture toughness were measured as a function of crystallized volume fraction for a constant crystal size. Glass-ceramics with a crystalline volume fraction between 34% and 60% exhibited a three-fold improvement in fracture strength and an increase of 40% in indentation fracture toughness compared with the parent glass. For the optimal crystalline concentration (34% and 60%) these mechanical properties were then measured for different grain sizes, from 5 to 21 μm. The glass-ceramic with the highest fracture strength and indentation fracture toughness was that with 34% crystallized volume fracture and 13 μm crystals. Compared with the parent glass, the average fracture strength of this glass-ceramic was increased from 80 to 210 MPa, and the fracture toughness from 0.60 to 0.95 MPa.m(1/2). The increase in indentation fracture toughness was analyzed using different theoretical models, which demonstrated that it is due to crack deflection. Fortunately, the elastic modulus E increased only slightly; from 60 to 70 GPa (the elastic modulus of biomaterials should be as close as possible to that of cortical bone). In summary, the flexural strength of our best material (215 MPa) is significantly greater than that of cortical bone and comparable with that of apatite-wollastonite (A/W) bioglass ceramics, with the advantage that it shows a much lower elastic modulus. These results thus provide a relevant guide for the design of bioactive glass-ceramics with improved microstructure. Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Iron Isotope Fractionation in the Bushveld Igneous Complex Provide Insight into Fractional Crystallization

NASA Astrophysics Data System (ADS)

Rios, K. L.; Feineman, M. D.; Bybee, G. M.

2016-12-01

Dated at 2.056 Ga and encompassing an estimated 65,000 km2 in surface area and 650,000 km3 in volume the Bushveld Igneous Complex in South Africa contains the largest and most unique layered mafic intrusion in the world. It contains 80-90% of the world's minable platinum group elements. Scientists are interested in understanding the origin of this intrusion due to its massive size, unique assemblage of minerals, and strongly zoned stratigraphy. Iron isotopes may help us to understand the roles of partial mantle melting and fractional crystallization in magma genesis and differentiation. For example, it may be possible to determine what role fractional crystallization of oxides and sulfides played in the formation of the Rustenburg Layered Suite (RLS) by comparing δ56Fe in samples from the Lower, Critical, Main and Upper Zones. The use of MC-ICPMS has made it more routine to study the fractionation of stable iron isotopes in natural systems; however, this technique has only been applied in a few studies of the RLS, mostly restricted to the Upper Main and Upper Zones. In this study δ56Fe was determined in Upper Zone magnetite, Critical Zone chromitite and Critical Zone sulfides using MC-ICP-MS. Previous research has shown that early crystallizing mafic phases incorporate the lighter 54Fe isotope leaving a residual magma with a higher δ56Fe value. Therefore, if the Upper Zone magma represents a high-degree differentiate of the parental Bushveld magma, then magmas from the Upper Zone would be expected to have a higher δ56Fe than magmas contributing to the Lower, Critical and Main Zones. The results of this experiment were indeed consistent with this hypothesis. The δ56Fe values recorded for the three sample types were: magnetite 0.19 ±0.03‰; sulfides -0.45 ±0.03‰ to -0.81 ±0.03‰; and chromitite 0.03 ±0.05‰. The sulfides of the Critical Zone are isotopically lighter than would be predicted based on equilibrium sulfide-melt fractionation, if the parental melt of the Critical Zone were in equilibrium with previously published whole rock data for Upper Zone. This is consistent with interpretations of the Upper Zone as a high degree differentiate of the Bushveld Parental Magma.

Crystallization kinetics of the Cu{sub 50}Zr{sub 50} metallic glass under isothermal conditions

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

Gao, Qian; Jian, Zengyun, E-mail: jianzengyun@xatu.edu.cn; Xu, Junfeng

2016-12-15

Amorphous structure of the melt-spun Cu{sub 50}Zr{sub 50} amorphous alloy ribbons were confirmed by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HR-TEM). Isothermal crystallization kinetics of these alloy ribbons were investigated using differential scanning calorimetry (DSC). Besides, Arrhenius and Johnson-Mehl-Avrami (JMA) equations were utilized to obtain the isothermal crystallization kinetic parameters. As shown in the results, the local activation energy E{sub α} decreases by a large margin at the crystallized volume fraction α<0.1, which proves that crystallization process is increasingly easy. In addition, the local activation energy E{sub α} is basically constant at 0.1

Microgravity

NASA Image and Video Library

2004-04-15

This is an image of a colloidal crystal from the CDOT-2 investigation flown on STS-95. There are so many colloidal particles in this sample that it behaves like a glass. In the laboratory on Earth, the sample remained in an amorphous state, showing no sign of crystal growth. In microgravity the sample crystallized in 3 days, as did the other glassy colloidal samples examined in the CDOT-2 experiment. During the investigation, crystallization occurred in samples that had a volume fraction (number of particles per total volume) larger than the formerly reported glass transition of 0.58. This has great implications for theories of the structural glass transition. These crystals were strong enough to survive space shuttle re-entry and landing.

Geochronology, geochemistry, and Sr-Nd-Pb-Hf isotopes of the Zhunsujihua granitoid intrusions associated with the molybdenum deposit, northern Inner Mongolia, China: implications for petrogenesis and tectonic setting

NASA Astrophysics Data System (ADS)

Zhang, Xiaojun; Lentz, David R.; Yao, Chunliang; Liu, Rui; Yang, Zhen; Mei, Yanxiong; Fan, Xianwang; Huang, Fei; Qin, Ying; Zhang, Kun; Zhang, Zhenfei

2018-03-01

The Zhunsujihua porphyry molybdenum deposit, located in northern Inner Mongolia of China that belongs to Central-Asian Orogenic Belt (CAOB), is the only Mo deposit formed in the late Carboniferous in this area so far. Its mineralization is mainly restricted to the Zhunsujihua granitoid intrusions, which are composed of the main granodiorite (GD) and crosscutting, virtually coeval minor syn-ore leucogranite (LG) and diorite porphyry (DP) dykes. LA-ICP-MS zircon U-Pb dating yields crystallization ages of 300.0 ± 2.0, 299.3 ± 2.0, and 299.0 ± 2.6 Ma for the GD, LG, and DP, respectively. The major and trace element lithogeochemical data show that the GD and LG are metaluminous to weakly peraluminous, high-K calc-alkaline series with I-type granite characteristics, strongly oxidized, with low concentrations of Ba, Nb, Sr, P, and Ti and elevated K and Rb contents, indicating typical arc magmatic features. The LG is a product derived by extensive fractional crystallization of a parental magma similar to the GD as evident from the lower Eu/Eu*, Nb/Ta, Zr/Hf, and T Zr. The moderately altered DP exhibits high concentrations of K, Rb, Cs, LREE, Y, and low Sr/Y, with a positive ɛ Nd (300 Ma), which indicates a mantle or juvenile source associated with an arc setting. The Sr-Nd-Hf isotope data show low I Sr (0.70406-0.70461) and moderate ɛ Nd (300 Ma) (-0.9 to 1.5) for the GD and LG, and relatively high ɛ Hf (300 Ma) values (-3.6 to +11.2) for the GD, suggesting the magma mainly originated from the juvenile lower crust that was derived from depleted mantle, with a minor component of ancient continental crust. Lead isotope data have characteristics of a lower crust source with minor contamination by upper crustal material. Combined with previous research, the Zhunsujihua granitoid intrusions developed in an intracontinental volcanic arc (Uliastai) associated with northward subduction of the Paleo-Asian Ocean plate during late Carboniferous to early Permian; this suggests that the subduction of Paleo Asian Ocean may have continued to late Carboniferous, and the Hengenshan basin is probably closed during the early Permian. Fractional crystallization is the main evolutionary process of the felsic magma, which has played an important role in the Mo mineralization. The coeval DP may have provided additional heat for the extended evolution of the crystallizing felsic magma chamber.

Filling-Fraction Fluctuation Leading to Glasslike Ultralow Thermal Conductivity in Caged Skutterudites

NASA Astrophysics Data System (ADS)

Ren, Wei; Geng, Huiyuan; Zhang, Zihao; Zhang, Lixia

2017-06-01

It is generally believed that filling atoms randomly and uniformly distribute in caged crystals, such as skutterudite compounds. Here, we report first-principles and experimental discovery of a multiscale filling-fraction fluctuation in the R Fe4Sb12 system. La0.8Ti0.1Ga0.1Fe4Sb12 spontaneously separates into La-rich and La-poor skutterudite phases, leading to multiscale strain field fluctuations. As a result, glasslike ultralow lattice thermal conductivity approaching the theoretical minimum is achieved, mainly due to strain field scattering of high-energy phonons. These findings reveal that an uneven distribution of filling atoms is efficient to further reduce the lattice thermal conductivity of caged crystals.

Pre-K-8 Prospective Teachers' Understanding of Fractions: An Extension of Fractions Schemes and Operations Research

ERIC Educational Resources Information Center

Lovin, LouAnn H.; Stevens, Alexis L.; Siegfried, John; Wilkins, Jesse L. M.; Norton, Anderson

2018-01-01

In an effort to expand our knowledge base pertaining to pre-K-8 prospective teachers' understanding of fractions, the present study was designed to extend the work on fractions schemes and operations to this population. One purpose of our study was to validate the fractions schemes and operations hierarchy with the pre-K-8 prospective teacher…

Propagation of optical vortices with fractional topological charge in free space

NASA Astrophysics Data System (ADS)

Ali, Tamelia; Kreminska, Liubov; Golovin, Andrii B.; Crouse, David T.

2014-10-01

The behavior of the optical vortices with fractional topological charges in the far-field is assessed through numerical modeling and confirmed by experimental results. The generation of fractional topological charge variations of the phase within a Gaussian beam was achieved by using a liquid crystal spatial light modulator (LCoS SLM). It is shown that a laser beam carrying an optical vortex with a fractional topological charge evolves into a beam with a topological charge of integer value, specifically an integer value closer to the fractional number in the far field. A potential application of this work is for data transmission within optical telecommunication systems.

Geometrical Characteristics of Cd-Rich Inclusion Defects in CdZnTe Materials

NASA Astrophysics Data System (ADS)

Xu, Chao; Sheng, Fengfeng; Yang, Jianrong

2017-08-01

The geometrical characteristics of Cd-rich inclusion defects in CdZnTe crystals have been investigated by infrared transmission (IRT) microscopy and chemical etching methods, revealing that they are composed of a Cd-rich inclusion core zone with high dislocation density and defect extension belts. Based on the experimental results, the orientation and shape of these belts were determined, showing that their extension directions in three-dimensional (3-D) space are along <211> crystal orientation. To explain the observed IRT images of Cd-rich inclusion defects, a 3-D model with plate-shaped structure for dislocation extension belts is proposed. Greyscale IRT images of dislocation extension belts thus depend on their absorption layer thickness. Assuming that defects can be discerned by IRT microscopy only when their absorption layer thickness is greater than twice that of the plate-shaped dislocation extension belts, this 3-D defect model can rationalize the IRT images of Cd-rich inclusion defects.

Deliquescence and crystallization of ammonium sulfate-glutaric acid and sodium chloride-glutaric acid particles

NASA Astrophysics Data System (ADS)

Pant, Atul; Fok, Abel; Parsons, Matthew T.; Mak, Jackson; Bertram, Allan K.

2004-06-01

In the following, we report the deliquescence relative humidities (DRH) and crystallization relative humidities (CRH) of mixed inorganic-organic particles, specifically ammonium sulfate-glutaric acid and sodium chloride-glutaric acid particles. Knowledge of the DRH and CRH of mixed inorganic-organic particles is crucial for predicting the role of aerosol particles in the atmosphere. Our DRH results are in good agreement with previous measurements, but our CRH results are significantly lower than some of the previous measurements reported in the literature. Our studies show that the DRH and CRH of ammonium sulfate and sodium chloride only decreased slightly when the mole fraction of the acid was less than 0.4. If other organics in the atmosphere behave in a similar manner, then the DRH and CRH of mixed inorganic-organic atmospheric particles will only be slightly less than the DRH and CRH of pure inorganic particles when the organic mole fraction is less than 0.4. Our results also show that if the particles contain a significant amount of organics (mole fraction > 0.5) the crystallization relative humidity decreases significantly and the particles are more likely to remain in the liquid state. Further work is needed to determine if other organics species of atmospheric importance have a similar effect.

Bacterially induced mineralization of calcium carbonate: the role of exopolysaccharides and capsular polysaccharides.

PubMed

Ercole, Claudia; Cacchio, Paola; Botta, Anna Lucia; Centi, Valeria; Lepidi, Aldo

2007-02-01

Bacterially induced carbonate mineralization has been proposed as a new method for the restoration of limestones in historic buildings and monuments. We describe here the formation of calcite crystals by extracellular polymeric substances isolated from Bacillus firmus and Bacillus sphaericus. We isolated bacterial outer structures (glycocalix and parietal polymers), such as exopolysaccharides (EPS) and capsular polysaccharides (CPS) and checked for their influence on calcite precipitation. CPS and EPS extracted from both B. firmus and B. sphaericus were able to mediate CaCO3 precipitation in vitro. X-ray microanalysis showed that in all cases the formed crystals were calcite. Scanning electron microscopy showed that the shape of the crystals depended on the fractions utilized. These results suggest the possibility that biochemical composition of CPS or EPS influences the resulting morphology of CaCO3. There were no precipitates in the blank samples. CPS and EPS comprised of proteins and glycoproteins. Positive alcian blue staining also reveals acidic polysaccharides in CPS and EPS fractions. Proteins with molecular masses of 25-40 kDa and 70 kDa in the CPS fraction were highly expressed in the presence of calcium oxalate. This high level of synthesis could be related to the binding of calcium ions and carbonate deposition.

Molybdenite tricks with titanite give history of the Central Indian Tectonic Zone

NASA Astrophysics Data System (ADS)

Stein, Holly J.; Hannah, Judith L.; Pandit, Manoj K.; Mohanty, Saradaprasad; Corfu, Fernando; Zimmerman, Aaron

2014-05-01

The time that the cratonic blocks joined to form peninsular India creating the E-W-trending Central Indian Tectonic Zone (CITZ) is important for tectonic reconstructions and Paleoproterozoic glaciations, and fundamental to understanding how sutures behave through time. An abundance of recent literature highlights ~1.0 Ga as the time of suturing. This late 1.0 Ga meeting of the two cratons, however, is increasingly difficult to reconcile. One of the well-studied and well-mapped terranes in the southern part of the CITZ is the Sausar Belt [1]. The metasedimentary and metavolcanic rocks comprising the extensive Paleoproterozoic Sausar Group are multiply deformed. To examine the history of the Sausar Belt from a new vantage, we employed Re-Os dating of molybdenite, a sulfide that serves faithfully as a single-mineral radiometric clock in both magmatic and metamorphic environments [2]. Molybdenite is rare in the Sausar belt. Samples containing a 1-cm molybdenite patch and coarse-grained, euhedral, clear brown titanite were acquired from two different varieties of calc-silicate rocks near the village of Umri in central India. The molybdenite occurs in a calcite-quartz vein that clearly cross-cuts a strongly deformed calc-silicate host with quartz-biotite and quartz bands at the cm scale. This vein, metamorphic in character, is about 1-cm-wide and slightly deformed. The molybdenite was contained wholly within the vein. To check for possible Re-Os decoupling [2], we split the molybdenite patch into seven subsamples, analyzing each fraction separately; in sum, these seven fractions account for the entire molybdenite crystal. We obtained extremely disparate ages for the individual fractions, ranging from 1.4 to 3.1 Ga. These data were recombined on an atomic basis to calculate the Re-Os age for the entire crystal, a trick we employed after affirming there was no additional sulfide and no additional molybdenite that might compete for Re and Os in our hand-sample of 10 x 15 cm. This circumstance provided us the opportunity to turn Re-Os decoupling to our advantage. The whole-crystal Re-Os molybdenite age on combining data from individual separates is between 2.41 and 2.45 Ga, depending on estimates of very minor silicate dilution as the crystal was extracted piecemeal from the vein. The U-Pb age for euhedral titanite crystals in a dense massive calc-silicate host, not unexpectedly, is ~1.0 Ga. The molybdenite and titanite record two different episodes of metamorphism. These results suggest that the Sausar Group calc-silicate rocks we analyzed are earliest Paleoproterozoic, >2.41 Ga. Shortly after deposition these rocks were metamorphosed - the first event in a long history of metamorphism and deformation continually focused along an ancient suture. These results have implications for the CITZ, and are similar to ages found in terranes on either side of this continental scale collisional belt [3,4]. This study was funded by the U.S. National Science Foundation (EAR-1119655). References Cited [1] Mohanty, S. (2010) Journal of Asian Earth Sciences 39: 516-526. [2] Stein et al. (2003) Geochimica et Cosmochimica Acta 67: 3673-3686. [3] Stein et al. (2004) Precambrian Research 134: 189-226. [4] Radhakrishna et al. (2013) Precambrian Research 226: 91-104.

Life Prediction of Turbine Blade Nickel Base Superalloy Single Crystals.

DTIC Science & Technology

1986-08-01

mechanical properties between single crystals and the DS version of Mar-M200. Soon it was recognized again through the mechanical property - structure ... property achievements demonstrated by screening and simulated engine tests. 1 Single crystals are the results of extensive investigation on the mechanical ...behavior, (especially fatigue and creep) of, and the structure - property correlations in the equiaxed and directionally solidified (DS) nickel-base

Energy-Constrained Recharge, Assimilation, and Fractional Crystallization (EC-RAχFC): A Visual Basic computer code for calculating trace element and isotope variations of open-system magmatic systems

NASA Astrophysics Data System (ADS)

Bohrson, Wendy A.; Spera, Frank J.

2007-11-01

Volcanic and plutonic rocks provide abundant evidence for complex processes that occur in magma storage and transport systems. The fingerprint of these processes, which include fractional crystallization, assimilation, and magma recharge, is captured in petrologic and geochemical characteristics of suites of cogenetic rocks. Quantitatively evaluating the relative contributions of each process requires integration of mass, species, and energy constraints, applied in a self-consistent way. The energy-constrained model Energy-Constrained Recharge, Assimilation, and Fractional Crystallization (EC-RaχFC) tracks the trace element and isotopic evolution of a magmatic system (melt + solids) undergoing simultaneous fractional crystallization, recharge, and assimilation. Mass, thermal, and compositional (trace element and isotope) output is provided for melt in the magma body, cumulates, enclaves, and anatectic (i.e., country rock) melt. Theory of the EC computational method has been presented by Spera and Bohrson (2001, 2002, 2004), and applications to natural systems have been elucidated by Bohrson and Spera (2001, 2003) and Fowler et al. (2004). The purpose of this contribution is to make the final version of the EC-RAχFC computer code available and to provide instructions for code implementation, description of input and output parameters, and estimates of typical values for some input parameters. A brief discussion highlights measures by which the user may evaluate the quality of the output and also provides some guidelines for implementing nonlinear productivity functions. The EC-RAχFC computer code is written in Visual Basic, the programming language of Excel. The code therefore launches in Excel and is compatible with both PC and MAC platforms. The code is available on the authors' Web sites http://magma.geol.ucsb.edu/and http://www.geology.cwu.edu/ecrafc) as well as in the auxiliary material.

Tectonic control on the genesis of magmas in the New Hebrides arc (Vanuatu)

NASA Astrophysics Data System (ADS)

Beier, Christoph; Brandl, Philipp A.; Lima, Selma M.; Haase, Karsten M.

2018-07-01

We present here new bathymetric, petrological and geochemical whole rock, glass and mineral data from the submarine Epi volcano in the New Hebrides (Vanuatu) island arc. The structure has previously been interpreted to be part of a larger caldera structure but new bathymetric data reveal that the volcanic cones are aligned along shear zones controlled by the local tectonic stress field parallel to the recent direction of subduction. We aim to test if there is an interaction between local tectonics and magmatism and to what extent the compositions of island arc volcanoes may be influenced by their tectonic setting. Primitive submarine Epi lavas and those from the neighbouring Lopevi and Ambrym islands originate from a depleted mantle wedge modified by addition of subduction zone components. Incompatible element ratios sensitive to fluid input (e.g., Th/Nb, Ce/Yb) in the lavas are positively correlated with those more sensitive to mantle wedge depletion (e.g., Nb/Yb, Zr/Nb) amongst the arc volcanoes suggesting that fluids or melts from the subducting sediments have a stronger impact on the more depleted compositions of the mantle wedge. The whole rock, glass and mineral major and trace element compositions and the occurrence of exclusively normally zoned clinopyroxene and plagioclase crystals combined with the absence of inversely zoned crystals and water-bearing phases in both mafic and evolved lavas suggest that the erupted melt was relatively dry compared to other subduction zone melts and has experienced little disequilibrium modification by melt mixing or assimilation. Our data also imply that differentiation of amphibole is not required to explain the incompatible element patterns but may rather result from extensive clinopyroxene fractionation in agreement with petrographic observations. Thermobarometric calculations indicate that the melts fractionated continuously during ascent, contrasting with fractionation during stagnation in an established crustal magma reservoir. We interpret the occurrence of this fractional crystallisation end-member in a relatively thick island arc crust ( 30 km thickness) to result from isolated and relatively rapid ascent of melts, most likely through a complex system of dykes and sills that developed due to the tectonic positioning of Epi in a complex tectonic zone between a compressional environment in the north and an extensional setting in the south. We can show that the alignment of the cones largely depends on the local tectonic stress field at Epi that is especially influenced by a large dextral strike-slip zone, indicating that structural features have a significant impact on the location and composition of volcanic edifices.

Predicting the mineral composition of dust aerosols – Part 1: Representing key processes

DOE PAGES

Perlwitz, J. P.; Perez Garcia-Pando, C.; Miller, R. L.

2015-10-21

Soil dust aerosols created by wind erosion are typically assigned globally uniform physical and chemical properties within Earth system models, despite known regional variations in the mineral content of the parent soil. Mineral composition of the aerosol particles is important to their interaction with climate, including shortwave absorption and radiative forcing, nucleation of cloud droplets and ice crystals, heterogeneous formation of sulfates and nitrates, and atmospheric processing of iron into bioavailable forms that increase the productivity of marine phytoplankton. Here, aerosol mineral composition is derived by extending a method that provides the composition of a wet-sieved soil. The extension accountsmore » for measurements showing significant differences between the mineral fractions of the wet-sieved soil and the emitted aerosol concentration. For example, some phyllosilicate aerosols are more prevalent at silt sizes, even though they are nearly absent at these diameters in a soil whose aggregates are dispersed by wet sieving. We calculate the emitted mass of each mineral with respect to size by accounting for the disintegration of soil aggregates during wet sieving. These aggregates are emitted during mobilization and fragmentation of the original undispersed soil that is subject to wind erosion. The emitted aggregates are carried far downwind from their parent soil. The soil mineral fractions used to calculate the aggregates also include larger particles that are suspended only in the vicinity of the source. We calculate the emitted size distribution of these particles using a normalized distribution derived from aerosol measurements. In addition, a method is proposed for mixing minerals with small impurities composed of iron oxides. These mixtures are important for transporting iron far from the dust source, because pure iron oxides are more dense and vulnerable to gravitational removal than most minerals comprising dust aerosols. Finally, a limited comparison to measurements from North Africa shows that the model extensions result in better agreement, consistent with a more extensive comparison to global observations as well as measurements of elemental composition downwind of the Sahara, as described in companion articles.« less

Dual exposure, two-photon, conformal phasemask lithography for three dimensional silicon inverse woodpile photonic crystals

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

Shir, Daniel J.; Nelson, Erik C.; Chanda, Debashis

2010-01-01

The authors describe the fabrication and characterization of three dimensional silicon inverse woodpile photonic crystals. A dual exposure, two-photon, conformal phasemask technique is used to create high quality polymer woodpile structures over large areas with geometries that quantitatively match expectations based on optical simulations. Depositing silicon into these templates followed by the removal of the polymer results in silicon inverse woodpile photonic crystals for which calculations indicate a wide, complete photonic bandgap over a range of structural fill fractions. Spectroscopic measurements of normal incidence reflection from both the polymer and siliconphotonic crystals reveal good optical properties.

Nepheline structural and chemical dependence on melt composition

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

Marcial, José; Crum, Jarrod; Neill, Owen

Nepheline crystallizes upon slow-cooling in some melts concentrated in Na2O and Al2O3, which can result in a residual glass phase of low chemical durability. Nepheline can incorporate many components often found in high-level waste radioactive borosilicate glass, including glass network ions (e.g., Si, Al, Fe), alkali metals (e.g., Cs, K, Na, and possibly Li), alkaline-earth metals (e.g., Ba, Sr, Ca, Mg), and transition metals (e.g., Mn, and possibly Cr, Zn, Ni). When crystallized from melts of different compositions, nepheline chemistry varies as a function of starting glass composition. Five simulated high level nuclear waste borosilicate glasses shown to crystallize largemore » fractions of nepheline on slow cooling, were selected for study. These melts constituted a range of Al2O3, B2O3, CaO, Na2O, K2O, Fe2O3, and SiO2 compositions. Compositional analyses of nepheline crystals in glass by electron probe micro-analysis (EPMA) indicate that boron is unlikely to be present in any significant concentration, if at all, in nepheline. Also, several models are presented for calculating the fraction of vacancies in the nepheline structure.« less

Auger electron spectroscopy analysis for growth interface of cubic boron nitride single crystals synthesized under high pressure and high temperature

NASA Astrophysics Data System (ADS)

Lv, Meizhe; Xu, Bin; Cai, Lichao; Guo, Xiaofei; Yuan, Xingdong

2018-05-01

After rapid cooling, cubic boron nitride (c-BN) single crystals synthesized under high pressure and high temperature (HPHT) are wrapped in the white film powders which are defined as growth interface. In order to make clear that the transition mechanism of c-BN single crystals, the variation of B and N atomic hybrid states in the growth interface is analyzed with the help of auger electron spectroscopy in the Li-based system. It is found that the sp2 fractions of B and N atoms decreases, and their sp3 fractions increases from the outer to the inner in the growth interface. In addition, Lithium nitride (Li3N) are not found in the growth interface by X-ray diffraction (XRD) experiment. It is suggested that lithium boron nitride (Li3BN2) is produced by the reaction of hexagonal boron nitride (h-BN) and Li3N at the first step, and then B and N atoms transform from sp2 into sp3 state with the catalysis of Li3BN2 in c-BN single crystals synthesis process.

Compositional modes in the ash fraction of some modern pyroclastic deposits: their determination and significance

NASA Astrophysics Data System (ADS)

De Rosa, R.

This paper illustrates some problems involved in the quantitative compositional study of pyroclastic deposits and proposes criteria for selecting the main petrographic and textural classes for modal analysis. The relative proportions of the different classes are obtained using a point-counting procedure applied to medium-coarse ash samples that reduces the dependence of the modal composition on grain size and avoids tedious counting of different grain-size fractions. The major purposes of a quantified measure of component distributions are to: (a) document the nature of the fragmenting magma; (b) define the eruptive dynamics of the eruptions on a detailed scale; and (c) ensure accuracy in classifying pyroclastic deposits. Compositional modes of the ash fraction of pyroclastic deposits vary systematically, and their graphical representation defines the compositional and textural characteristics of pyroclastic fragments associated with different eruptive styles. Textural features of the glass component can be very helpful for inferring aspects of eruptive dynamics. Four major parameters can be used to represent the component composition of pyroclastic ash deposits: (a) juvenile index (JI); (b) crystallinity index (CrI); (c) juvenile vesicularity index (JVI); and (d) free crystal index (FCrI). The FCrI is defined as the ratio between single and total crystal fragments in the juvenile component (single crystals+crystals in juvenile glass). This parameter may provide an effective estimate of the mechanical energy of eruptions. Variations in FCrI vs JVI discriminate among pyroclastic deposits of different origin and define compositional fields that represent ash derived from different fragmentation styles.

Defect chemistry and characterization Hg(1-x)Cd(x)Te

NASA Technical Reports Server (NTRS)

Vydyanath, H. R.; Donovan, J. C.

1981-01-01

Iodine doped single crystal samples of mercury cadmium telluride were annealed at temperatures varying from 450 C to 600 C in Hg vapor and quenched to room temperature. Hall effect measurements at 77 K on the crystals cooled to room temperature indicate the samples to be n-type after anneals at high Hg pressures whereas they turn p-type after anneals at low Hg pressures; the electron concentration increases with increase in Hg pressure. The results are explained on the basis that the crystals are saturated with (Hg,Cd)I2, with a fraction of the iodine being present as donor occupying tellurium lattice sites and a fraction being present as acceptors resulting from the iodine on tellurium lattice sites pairing with the doubly ionized native acceptor defects. The solubility of the donor species increases with increase in Hg pressure, whereas that of the acceptor species increases with decrease in Hg pressure. Equilibrium constants for the incorporation of the iodine species as well as the pairing reaction were established.

Crystallization of spin superlattices with pressure and field in the layered magnet SrCu 2(BO 3) 2

DOE PAGES

Haravifard, S.; Graf, D.; Feiguin, A. E.; ...

2016-06-20

An exact mapping between quantum spins and boson gases provides fresh approaches to the creation of quantum condensates and crystals. Here we report on magnetization measurements on the dimerized quantum magnet SrCu 2(BO 3) 2 at cryogenic temperatures and through a quantum-phase transition that demonstrate the emergence of fractionally filled bosonic crystals in mesoscopic patterns, specified by a sequence of magnetization plateaus. We apply tens of Teslas of magnetic field to tune the density of bosons and gigapascals of hydrostatic pressure to regulate the underlying interactions. Simulations help parse the balance between energy and geometry in the emergent spin superlattices.more » In conclusion, the magnetic crystallites are the end result of a progression from a direct product of singlet states in each short dimer at zero field to preferred filling fractions of spin-triplet bosons in each dimer at large magnetic field, enriching the known possibilities for collective states in both quantum spin and atomic systems.« less

Quantitative determination of zero-gravity effects on electronic materials processing germanium crystal growth with simultaneous interface demarcation experiment MA-060, section 5

NASA Technical Reports Server (NTRS)

Gatos, H. C.; Witt, A. F.; Lichtensteiger, M.; Herman, C. J.

1982-01-01

The crystal growth and segregation characteristics of a melt in a directional solidification configuration under near zero g conditions were investigated. The germanium (doped with gallium) system was selected because it was extensively studied on Earth and because it lends itself to a very detailed macroscopic and microscopic characterization. An extensive study was performed of the germanium crystals grown during the Apollo-Soyuz Test Project mission. It was found that single crystal growth was achieved and that the interface demarcation functioned successfully. On the basis of the results obtained to date, there is no indication that convection driven by thermal or surface tension gradients was present in the melt. The gallium segregation, in the absence of gravity, was found to be fundamentally different in its initial and its subsequent stages from that of the ground based tests. None of the existing theoretical models for growth and segregation can account for the observed segregation behavior in the absence of gravity.

Crystallization and preliminary X-ray analysis of membrane-bound pyrophosphatases.

PubMed

Kellosalo, Juho; Kajander, Tommi; Honkanen, Riina; Goldman, Adrian

2013-02-01

Membrane-bound pyrophosphatases (M-PPases) are enzymes that enhance the survival of plants, protozoans and prokaryotes in energy constraining stress conditions. These proteins use pyrophosphate, a waste product of cellular metabolism, as an energy source for sodium or proton pumping. To study the structure and function of these enzymes we have crystallized two membrane-bound pyrophosphatases recombinantly produced in Saccharomyces cerevisae: the sodium pumping enzyme of Thermotoga maritima (TmPPase) and the proton pumping enzyme of Pyrobaculum aerophilum (PaPPase). Extensive crystal optimization has allowed us to grow crystals of TmPPase that diffract to a resolution of 2.6 Å. The decisive step in this optimization was in-column detergent exchange during the two-step purification procedure. Dodecyl maltoside was used for high temperature solubilization of TmPPase and then exchanged to a series of different detergents. After extensive screening, the new detergent, octyl glucose neopentyl glycol, was found to be the optimal for TmPPase but not PaPPase.

Crystal Growth of ZnSe and Related Ternary Compound Semiconductors by Vapor Transport in Low Gravity

NASA Technical Reports Server (NTRS)

Su, Ching-Hua; Ramachandran, N.

2013-01-01

Crystals of ZnSe and related ternary compounds, such as ZnSeS and ZnSeTe, will be grown by physical vapor transport in the Material Science Research Rack (MSRR) on International Space Station (ISS). The objective of the project is to determine the relative contributions of gravity-driven fluid flows to the compositional distribution, incorporation of impurities and defects, and deviation from stoichiometry observed in the crystals grown by vapor transport as results of buoyance-driven convection and growth interface fluctuations caused by irregular fluid-flows on Earth. The investigation consists of extensive ground-based experimental and theoretical research efforts and concurrent flight experimentation. The objectives of the ground-based studies are (1) obtain the experimental data and conduct the analyses required to define the optimum growth parameters for the flight experiments, (2) perfect various characterization techniques to establish the standard procedure for material characterization, (3) quantitatively establish the characteristics of the crystals grown on Earth as a basis for subsequent comparative evaluations of the crystals grown in a low-gravity environment and (4) develop theoretical and analytical methods required for such evaluations. ZnSe and related ternary compounds have been grown by vapor transport technique with real time in-situ non-invasive monitoring techniques. The grown crystals have been characterized extensively by various techniques to correlate the grown crystal properties with the growth conditions.

Predicting equilibrium uranium isotope fractionation in crystals and solution

NASA Astrophysics Data System (ADS)

Schauble, E. A.

2015-12-01

Despite the rapidly growing interest in using 238U/235U measurements as a proxy for changes in oxygen abundance in surface and near-surface environments, the present theoretical understanding of uranium isotope fractionation is limited to a few simple gas-phase molecules and analogues of dissolved species (e.g., 1,2,3). Understanding uranium isotope fractionation behavior in more complicated species, such as crystals and adsorption complexes, will help in the design and interpretation of experiments and field studies, and may suggest other uses for 38U/235U measurements. In this study, a recently developed first-principles method for estimating the nuclear volume component of field shift fractionation in crystals and complex molecular species (4) is combined with mass-dependent fractionation theory to predict equilibrium 38U/235U fractionations in aqueous and crystalline uranium compounds, including uraninite (UO2). The nuclear field shift effect, caused by the interaction of electrons with the finite volume of the positive charge distribution in uranium nuclei, is estimated using Density Functional Theory and the Projector Augmented Wave method (DFT-PAW). Tests against relativistic electronic structure calculations and Mössbauer isomer shift data indicate that the DFT-PAW method is reasonably accurate, while being much better suited to models of complex and crystalline species. Initial results confirm previous predictions that the nuclear volume effect overwhelms mass depdendent fractionation in U(VI)-U(IV) exchange reactions, leading to higher 238U/235U in U(IV) species (i.e., for UO2 xtal vs. UO22+aq, ln αNV ≈ +1.8‰ , ln αMD ≈ -0.8‰, ln αTotal ≈ +1.0‰ at 25ºC). UO2 and U(H2O)94+, are within ~0.4‰ of each other, while U(VI) species appear to be more variable. This suggests that speciation is likely to significantly affect natural uranium isotope fractionations, in addition to oxidation state. Tentatively, it appears that uranyl-type (UO22+-bearing) structures will tend to have higher 238U/235U than uranate-type structures that lack strong U=O bonds. References: 1. Bigeleisen (1996) JACS 118:3676; 2. Schauble (2006) Eos 87:V21B-0570; 3. Abe et al. (2008) J Chem Phys 128:144309, 129:164309, & Abe et al. (2010) J Chem Phys 133:044309; 4. Schauble (2013) PNAS 110:17714.

Supersite of immune vulnerability on the glycosylated face of HIV-1 envelope glycoprotein gp120

PubMed Central

Kong, Leopold; Lee, Jeong Hyun; Doores, Katie J.; Murin, Charles D.; Julien, Jean-Philippe; McBride, Ryan; Liu, Yan; Marozsan, Andre; Cupo, Albert; Klasse, Per-Johan; Hoffenberg, Simon; Caulfield, Michael; King, C. Richter; Hua, Yuanzi; Le, Khoa M.; Khayat, Reza; Deller, Marc C.; Clayton, Thomas; Tien, Henry; Feizi, Ten; Sanders, Rogier W.; Paulson, James C.; Moore, John P.; Stanfield, Robyn L.; Burton, Dennis R.; Ward, Andrew B.; Wilson, Ian A.

2013-01-01

A substantial fraction of broadly neutralizing antibodies (bnAbs) in certain HIV-infected donors recognizes glycan-dependent epitopes on HIV-1 gp120. Here, we elucidate how bnAb PGT 135 recognizes its Asn332 glycan-dependent epitope from its crystal structure with gp120, CD4 and Fab 17b at 3.1 Å resolution. PGT 135 interacts with glycans at Asn332, Asn392 and Asn386, using long CDR loops H1 and H3 to penetrate the glycan shield to access the gp120 protein surface. Electron microscopy reveals PGT 135 can accommodate the conformational and chemical diversity of gp120 glycans by altering its angle of engagement. The combined structural studies of PGT 135, PGT 128 and 2G12 show this Asn332-dependent epitope is highly accessible and much more extensive than initially appreciated, allowing for multiple binding modes and varied angles of approach, thereby representing a supersite of vulnerability for antibody neutralization. PMID:23708606

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

Sharma, Shailesh, E-mail: shailesh.sharma6@mail.dcu.ie; Impedans Limited, Chase House, City Junction Business Park, Northern Cross, D17 AK63, Dublin 17; Gahan, David, E-mail: david.gahan@impedans.com

A compact retarding field analyzer with embedded quartz crystal microbalance has been developed to measure deposition rate, ionized flux fraction, and ion energy distribution arriving at the substrate location. The sensor can be placed on grounded, electrically floating, or radio frequency (rf) biased electrodes. A calibration method is presented to compensate for temperature effects in the quartz crystal. The metal deposition rate, metal ionization fraction, and energy distribution of the ions arriving at the substrate location are investigated in an asymmetric bipolar pulsed dc magnetron sputtering reactor under grounded, floating, and rf biased conditions. The diagnostic presented in this researchmore » work does not suffer from complications caused by water cooling arrangements to maintain constant temperature and is an attractive technique for characterizing a thin film deposition system.« less

Evolution of rhyolitic magmas in the crustal magmatic system beneath the Taupo Volcanic Zone, New Zealand

NASA Astrophysics Data System (ADS)

Johnson, E. R.; Kamenetsky, V.; McPhie, J.; Wallace, P. J.

2009-12-01

The Taupo Volcanic Zone (TVZ) produces the most frequent rhyolitic eruptions on Earth. This volcanic arc is also characterized by bimodal volcanism, with eruptions of andesite (primarily in the NE and SW of the zone) and minor basalt. Here we use melt inclusions (MI) to investigate the magmatic evolution of rhyolites in the TVZ and their link to TVZ basalts. Our study focuses on recent (<50 ka) explosive rhyolitic eruptions, as well as several small-volume explosive basaltic eruptions, from the Okataina Volcanic Centre in the northern part of the TVZ. The rhyolitic melts of the TVZ are thought to be formed via fractionation of a basaltic parent plus assimilation of metasedimentary crust. Trace element data from our TVZ melt inclusions lend support to this idea, with constant ratios of incompatible trace elements (e.g., U/Th) in the TVZ basalts and rhyolites. Assuming that these elements are completely incompatible, we have calculated that the TVZ rhyolites can be produced by ~80% fractional crystallization of a basaltic parent. We have also used MI volatile contents to assess the pressures (and thus depths) in the crust of magma emplacement and differentiation. Both the TVZ rhyolites and basalts are volatile-rich. Quartz-hosted MI in the rhyolites typically contain 5.5- 7.6 wt% H2O and up to 2500 ppm Cl, and olivine-hosted MI in the basalts contain up to 4.5 wt% H2O and 1250 ppm Cl. The H2O concentrations imply crystallization pressures of at least 200-440 MPa for the rhyolites, which correspond to depths of ~8-16 km. However, the presence of rhyolitic MI with lower H2O (3.5-5 wt%) suggests that crystallization may have occurred over a wide range of pressures. Additionally, the basalts erupted in the TVZ likely crystallized at minimum pressures of 100-200 MPa. Together, this suggests that basaltic and rhyolitic melt zones occur over a wide range of depths (~4-16 km). Furthermore, the emplacement of the basaltic parent and the AFC process to create the rhyolites had to occur at depths >8-16 km. Our findings are consistent with geophysical models which suggest partial melts are present at depths of 6-16 km beneath portions of the TVZ (Bannister et al., 2004). We have also used MI analyses and cathodoluminescence (CL) images of quartz to assess degassing, mixing and fractionation in these magma systems. Our MI data indicate that the rhyolites underwent vapour-saturated crystallization. Concentrations of both H2O and Cl increase slightly during crystallization, suggesting that these volatiles behaved as moderately incompatible elements during fractionation. The extents of such fractionation are variable, and in some cases mixing of several rhyolitic magmas occurred, but in general we find that the range in U and Th in MI indicates ~7-20% crystallization from the least to most evolved rhyolitic melt. The results of this study provide important insights into the origin and evolution of rhyolitic magmas in an arc environment.

Syn-extensional emplacement of the 1. 42 Ga Sandia Granite, N. M

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

Karlstrom, K.E.; Kirby, E.; Andronicos, C.

1993-02-01

The 1.42 Ga Sandia pluton is one of a suite of Middle Proterozoic granitoid intrusions exposed in northern New Mexico. It crops out over 420 km[sup 2] in the Sandia Mountains, just east of Albuquerque. Recent structural work indicates that the pluton was emplaced syntectonically with respect to a transtensional ductile shear zone on its southeastern side. The shear zone is 1-2 km wide, dips 60[degree] NW under the pluton, and is thus inferred to be a deformed base or lower side of the pluton. From NW to SE, a transect across the zone consists of (1) essentially undeformed, locallymore » flow-foliated Sandia pluton (megacrystic monzogranite); (2) mylonitic, augen orthogneiss that is clearly sheared Sandia pluton; its matrix is depleted in quartz and K-feldspar and enriched in biotite relative to the undeformed pluton; (3) Cibola granite - a 1 km wide zone of fine to coarse grained, equigranular, leucocratic granite; (4) the Tijeras Fault - a Phanerozoic brittle fault; (5) the Tijeras Greenstone - unsheared amphibolite and interlayered pelitic schist and quartzite. Field and microstructural relationships indicate that pluton crystallization was synchronous with shear zone movements. Shear zone movement is interpreted to have punctuated segregation of evolved melts during fractional crystallization of the magma. Geochemical data show linear trends in major and trace elements, with compositional gaps between the main pluton and leucocratic phases. Strain studies suggest that the biotite-rich mylonitic augen orthogneiss records significant volume loss in the matrix. Melts presumably were drawn down pressure gradients into the active shear zone after the main unit was 50--70% crystallized. Further work is required to constrain whether extension was related to regional deformation or only to pluton emplacement.« less

Mmmagma: Edible Demonstrations of Magmatic Processes

NASA Astrophysics Data System (ADS)

Rust, A. C.; Cashman, K. V.; Wright, H. M.

2005-12-01

We present a collection of demonstrations using common foods to illustrate factors that influence bubble and crystal nucleation and growth in magmas, and consequences for volcanic processes. Using foods such as soda water, raisins, fudge, popcorn and cake, ensures that the demonstration are safe, cheap and can be repeated by students (with variations) in their own kitchens. From these experiments students learn about the influence of crystals and bubbles on magma rheology and permeability, and how these properties in turn affect lava flow morphologies, crystal fractionation, the formation of breadcrust bombs, and styles of volcanic eruptions.

Treatment of TNT red water by layer melt crystallization.

PubMed

Jo, Jeong-Hyeon; Ernest, Takyi; Kim, Kwang-Joo

2014-09-15

Treatment of the red water, which is wastewater of 2,4,6- trinitrotoluene (TNT) manufacturing process has been explored using ice crystallization. This study focuses on the formation of ice crystals from the red water in a layer crystallizer under various operating conditions. Among the parameters which affect layer crystallization, attention was given to cooling rate, cooling temperature, sweating rate and concentration of the red water. The study highlights the effect of subcooling and growth rate on purity of the ice crystalline layers produced. After sweating, the COD value of crystalline ice layer was significantly reduced from 10,000 mg/L to below 20mg/L. Most organic contaminants were removed in sweating fractions of 0.5. Eventually, the red water was treated by layer crystallization combined with the sweating process. Copyright © 2014 Elsevier B.V. All rights reserved.

Liquid-liquid diffusion crystallization improves the X-ray diffraction of EndoS, an endo-β-N-acetylglucosaminidase from Streptococcus pyogenes with activity on human IgG.

PubMed

Trastoy, Beatriz; Lomino, Joseph V; Wang, Lai Xi; Sundberg, Eric J

2013-12-01

Endoglycosidase S (EndoS) is an enzyme secreted by Streptococcus pyogenes that specifically hydrolyzes the β-1,4-di-N-acetylchitobiose core glycan on immunoglobulin G (IgG) antibodies. One of the most common human pathogens and the cause of group A streptococcal infections, S. pyogenes secretes EndoS in order to evade the host immune system by rendering IgG effector mechanisms dysfunctional. On account of its specificity for IgG, EndoS has also been used extensively for chemoenzymatic synthesis of homogeneous IgG glycoprotein preparations and is being developed as a novel therapeutic for a wide range of autoimmune diseases. The structural basis of its enzymatic activity and substrate specificity, however, remains unknown. Here, the purification and crystallization of EndoS are reported. Using traditional hanging-drop and sitting-drop vapor-diffusion crystallization, crystals of EndoS were grown that diffracted to a maximum of 3.5 Å resolution but suffered from severe anisotropy, the data from which could only be reasonably processed to 7.5 Å resolution. When EndoS was crystallized by liquid-liquid diffusion, it was possible to grow crystals with a different space group to those obtained by vapor diffusion. Crystals of wild-type endoglycosidase and glycosynthase constructs of EndoS grown by liquid-liquid diffusion diffracted to 2.6 and 1.9 Å resolution, respectively, with a greatly diminished anisotropy. Despite extensive efforts, the failure to reproduce these liquid-liquid diffusion-grown crystals by vapor diffusion suggests that these crystallization methods each sample a distinct crystallization space.

Mineral chemistry of the Tissint meteorite: Indications of two-stage crystallization in a closed system

NASA Astrophysics Data System (ADS)

Liu, Yang; Baziotis, Ioannis P.; Asimow, Paul D.; Bodnar, Robert J.; Taylor, Lawrence A.

2016-12-01

The Tissint meteorite is a geochemically depleted, olivine-phyric shergottite. Olivine megacrysts contain 300-600 μm cores with uniform Mg# ( 80 ± 1) followed by concentric zones of Fe-enrichment toward the rims. We applied a number of tests to distinguish the relationship of these megacrysts to the host rock. Major and trace element compositions of the Mg-rich core in olivine are in equilibrium with the bulk rock, within uncertainty, and rare earth element abundances of melt inclusions in Mg-rich olivines reported in the literature are similar to those of the bulk rock. Moreover, the P Kα intensity maps of two large olivine grains show no resorption between the uniform core and the rim. Taken together, these lines of evidence suggest the olivine megacrysts are phenocrysts. Among depleted olivine-phyric shergottites, Tissint is the first one that acts mostly as a closed system with olivine megacrysts being the phenocrysts. The texture and mineral chemistry of Tissint indicate a crystallization sequence of: olivine (Mg# 80 ± 1) → olivine (Mg# 76) + chromite → olivine (Mg# 74) + Ti-chromite → olivine (Mg# 74-63) + pyroxene (Mg# 76-65) + Cr-ulvöspinel → olivine (Mg# 63-35) + pyroxene (Mg# 65-60) + plagioclase, followed by late-stage ilmenite and phosphate. The crystallization of the Tissint meteorite likely occurred in two stages: uniform olivine cores likely crystallized under equilibrium conditions; and a fractional crystallization sequence that formed the rest of the rock. The two-stage crystallization without crystal settling is simulated using MELTS and the Tissint bulk composition, and can broadly reproduce the crystallization sequence and mineral chemistry measured in the Tissint samples. The transition between equilibrium and fractional crystallization is associated with a dramatic increase in cooling rate and might have been driven by an acceleration in the ascent rate or by encounter with a steep thermal gradient in the Martian crust.

Geochronology, geochemical and Sr-Nd-Hf-Pb isotopic compositions of the granitoids in the Yemaquan orefield, East Kunlun orogenic belt, northern Qinghai-Tibet Plateau: Implications for magmatic fractional crystallization and sub-solidus hydrothermal alteration

NASA Astrophysics Data System (ADS)

Yin, Shuo; Ma, Changqian; Xu, Jiannan

2017-12-01

A general consensus has emerged that high field strength elements (HFSE) can mobile to some extent in a hydrothermal fluid. However, there are hot debates on whether sub-solidus hydrothermal alteration can lower the Nb/Ta ratio in evolved melts. In this study, we present petrography, geochronology and geochemistry of the barren and mineralized rocks in the Yemaquan skarn iron deposit, northern Qinghai-Tibet Plateau, to probe magmatic-hydrothermal transition. The barren rocks consist of diorites, granodiorites, granites and syenogranites, whereas the porphyritic granodiorites are associated with mineralization for an excellent consistency between the magmatic zircon U-Pb age (225 ± 2 Ma) and the hydrothermal phlogopite 40Ar-39Ar age (225 ± 1.5 Ma). The Sr-Nd-Hf-Pb isotopic data demonstrate that the Yemaquan granitoids are originated from a relatively homogenous enriched mantle with different degrees of crust contamination (assimilation fractional crystallization, AFC). Trace elements signatures indicate that the porphyritic granodiorites related to mineralization display amphibole crystallization for high water contents, whereas the barren granites have gone through biotite crystallization due to potassium enrichment by continuous upper crust contamination, both of which are responsible for their Nb/Ta ratios, respectively. Modeling results suggest that a basaltic melt with Nb/Ta ratio of 15.3 can reach a minimum Nb/Ta ratio of 12 in the producing granodioritic melt by amphibole fractional crystallization based on partition coefficients of Nb and Ta between amphibole and melts from previous experiments. This may explain the average Nb/Ta ratio (13.7) of the barren granodiorites, while it cannot account for the average Nb/Ta ratio (8.4) of the mineralized porphyritic granodiorites, and it is even lower than that of the granites (10.3) with biotite fractional crystallization. Exsolution of a magmatic-hydrothermal fluid is inevitable when a water saturated magma emplaced in shallow crust, leading to a transportation of certain chemical components from the magmatic melts to exsolved fluids. Because Nb seems more mobile than Ta in fluorine-bearing fluids, we contend that a preferentially transport Nb over Ta by sub-solidus hydrothermal alteration can further lower the Nb/Ta ratios of the mineralized porphyritic granodiorites, which may also result in a broad range of HFSE contents and their ratios in the altered porphyritic granodiorites formed in a post-magmatic process.

On some new properties of fractional derivatives with Mittag-Leffler kernel

NASA Astrophysics Data System (ADS)

Baleanu, Dumitru; Fernandez, Arran

2018-06-01

We establish a new formula for the fractional derivative with Mittag-Leffler kernel, in the form of a series of Riemann-Liouville fractional integrals, which brings out more clearly the non-locality of fractional derivatives and is easier to handle for certain computational purposes. We also prove existence and uniqueness results for certain families of linear and nonlinear fractional ODEs defined using this fractional derivative. We consider the possibility of a semigroup property for these derivatives, and establish extensions of the product rule and chain rule, with an application to fractional mechanics.

Crystal growth of organics for nonlinear optical applications

NASA Technical Reports Server (NTRS)

Singh, N. B.; Mazelsky, R.

1993-01-01

The crystal growth and characterization of organic and inorganic nonlinear optical materials were extensively studied. For example, inorganic crystals such as thallium arsenic selenide were studied in our laboratory for several years and crystals in sizes over 2.5 cm in diameter are available. Organic crystals are suitable for the ultraviolet and near infrared region, but are relatively less developed than their inorganic counterparts. Very high values of the second harmonic conversion efficiency and the electro-optic coefficient were reported for organic compounds. Single crystals of a binary organic alloy based on m.NA and CNA were grown and higher second harmonic conversion efficiency than the values reported for m.NA were observed.

Crystal-free Formation of Non-Oxide Optical Fiber

NASA Technical Reports Server (NTRS)

Nabors, Sammy A.

2015-01-01

Researchers at NASA Marshall Space Flight Center have devised a method for the creation of crystal-free nonoxide optical fiber preforms. Non-oxide fiber optics are extensively used in infrared transmitting applications such as communication systems, chemical sensors, and laser fiber guides for cutting, welding and medical surgery. However, some of these glasses are very susceptible to crystallization. Even small crystals can lead to light scatter and a high attenuation coefficient, limiting their usefulness. NASA has developed a new method of non-oxide fiber formation that uses axial magnetic fields to suppress crystallization. The resulting non-oxide fibers are crystal free and have lower signal attenuation rates than silica based optical fibers.

Effect of local structures on crystallization in deeply undercooled metallic glass-forming liquids

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

Jiang, S. Q.; Li, M. Z., E-mail: maozhili@ruc.edu.cn; Wu, Z. W.

2016-04-21

The crystallization mechanism in deeply undercooled ZrCu metallic glass-forming liquids was investigated via molecular dynamics simulations. It was found that the crystallization process is mainly controlled by the growth of crystal nuclei formed by the BCC-like atomic clusters, consistent with experimental speculations. The crystallization rate is found to relate to the number of growing crystal nuclei in the crystallization process. The crystallization rate in systems with more crystal nuclei is significantly hindered by the larger surface fractions of crystal nuclei and their different crystalline orientations. It is further revealed that in the crystallization in deeply undercooled regions, the BCC-like crystalmore » nuclei are formed from the inside of the precursors formed by the FCC-like atomic clusters, and growing at the expense of the precursors. Meanwhile, the precursors are expanding at the expense of the outside atomic clusters. This process is consistent with the so-called Ostwald step rule. The atomic structures of metallic glasses are found to have significant impact on the subsequent crystallization process. In the Zr{sub 85}Cu{sub 15} system, the stronger spatial correlation of Cu atoms could hinder the crystallization processes in deeply undercooled regions.« less

Lunar Magma Ocean Crystallization: Constraints from Fractional Crystallization Experiments

NASA Technical Reports Server (NTRS)

Rapp, J. F.; Draper, D. S.

2015-01-01

The currently accepted paradigm of lunar formation is that of accretion from the ejecta of a giant impact, followed by crystallization of a global scale magma ocean. This model accounts for the formation of the anorthosite highlands crust, which is globally distributed and old, and the formation of the younger mare basalts which are derived from a source region that has experienced plagioclase extraction. Several attempts at modelling the crystallization of such a lunar magma ocean (LMO) have been made, but our ever-increasing knowledge of the lunar samples and surface have raised as many questions as these models have answered. Geodynamic models of lunar accretion suggest that shortly following accretion the bulk of the lunar mass was hot, likely at least above the solidus]. Models of LMO crystallization that assume a deep magma ocean are therefore geodynamically favorable, but they have been difficult to reconcile with a thick plagioclase-rich crust. A refractory element enriched bulk composition, a shallow magma ocean, or a combination of the two have been suggested as a way to produce enough plagioclase to account for the assumed thickness of the crust. Recently however, geophysical data from the GRAIL mission have indicated that the lunar anorthositic crust is not as thick as was initially estimated, which allows for both a deeper magma ocean and a bulk composition more similar to the terrestrial upper mantle. We report on experimental simulations of the fractional crystallization of a deep (approximately 100km) LMO with a terrestrial upper mantle-like (LPUM) bulk composition. Our experimental results will help to define the composition of the lunar crust and mantle cumulates, and allow us to consider important questions such as source regions of the mare basalts and Mg-suite, the role of mantle overturn after magma ocean crystallization and the nature of KREEP

The origin of plagioclase phenocrysts in basalts from continental monogenetic volcanoes of the Kaikohe-Bay of Islands field, New Zealand: implications for magmatic assembly and ascent

NASA Astrophysics Data System (ADS)

Coote, Alisha; Shane, Phil; Stirling, Claudine; Reid, Malcolm

2018-02-01

Late Quaternary, porphyritic basalts erupted in the Kaikohe-Bay of Islands area, New Zealand, provide an opportunity to explore the crystallization and ascent history of small volume magmas in an intra-continental monogenetic volcano field. The plagioclase phenocrysts represent a diverse crystal cargo. Most of the crystals have a rim growth that is compositionally similar to groundmass plagioclase ( An65) and is in equilibrium with the host basalt rock. The rims surround a resorbed core that is either less calcic ( An20-45) or more calcic (> An70), having crystallized in more differentiated or more primitive melts, respectively. The relic cores, particularly those that are less calcic (< An45), have 87Sr/86Sr ratios that are either mantle-like ( 0.7030) or crustal-like ( 0.7040 to 0.7060), indicating some are antecrysts formed in melts fractionated from plutonic basaltic forerunners, while others are true xenocrysts from greywacke basement and/or Miocene arc volcanics. It is envisaged that intrusive basaltic forerunners produced a zone where various degrees of crustal assimilation and fractional crystallization occurred. The erupted basalts represent mafic recharge of this system, as indicated by the final crystal rim growths around the entrained antecrystic and xenocrystic cargo. The recharge also entrained cognate gabbros that occur as inclusions, and produced mingled groundmasses. Multi-stage magmatic ascent and interaction is indicated, and is consistent with the presence of a partial melt body in the lower crust detected by geophysical methods. This crystallization history contrasts with traditional concepts of low-flux basaltic systems where rapid ascent from the mantle is inferred. From a hazards perspective, the magmatic system inferred here increases the likelihood of detecting eruption precursor phenomena such as seismicity, degassing and surface deformation.

Role of crystallizational differention in the origin of island-arc andesitic melts: evidence from data on melt inclusions and oxygen isotopes

NASA Astrophysics Data System (ADS)

Krasheninnikov, S. P.; Portnyagin, M.; Bindeman, I. N.; Bazanova, L. I.

2012-12-01

Several recent studies of melt inclusions in island-arc rocks revealed a strong bimodality of the melt compositions at the predominance of basic and silicic melts and the scarcity of intermediate melts with SiO2=59-66 wt% (e.g. [1]). These observations were used to interpret the origin of island-arc andesites by magma mingling, crustal assimilation and crystal accumulation rather than by fractional crystallization of basaltic magmas. In this work we addressed the question about the scarcity of andesitic melts in island-arc setting by systematic study of bulk compositions, melt inclusions and oxygen isotopes in minerals from Avachinskiy volcano in Kamchatka. We studied ~500 melt inclusions in 6 different mineral phases (Ol, Cpx, Opx, Pl, Amph, Mt), and concentrated on rapidly-quenched tephra samples from 40 Holocene eruptions of andesites and basaltic andesites. The melt inclusions span a large range of compositions from basalts to rhyolites. In comparison with host bulk tephra samples, melt inclusions tend to have more silicic compositions (up to 10 wt% of SiO2), and this disparity tend to increase with increasing SiO2 content in the host rocks. Both melt inclusion and host rock compositions form trends along the line dividing low- and middle-K island-arc series, and variations of major elements are continuous, without apparent bimodality, which is observed in data set from [1]. The MI statistical distribution is rather three-modal with maxima at ~56-58, ~66 and 74 wt% of SiO2. Much of the major element variability in MI can be explained by fractional crystallization from parental basaltic melts using numerical modeling of crystallization path. Magnetite crystallization starts at ~58 wt% of SiO2 and affects significantly on the evolutional path of melts. Abundant crystallization of magnetite lead to formation of more silica rich coexistent melts and change of crystallizing assemblage occurred at ~60 wt% of SiO2, when Opx replaced Ol, and Amph and Ap become stable. Paragenesis of OPx, CPx, Amph, Pl, Mt, Ilm and Ap dominated the following evolution of melts toward strongly acid compositions with 78-80 wt% SiO2. Individual Pl and Amph crystals are in magmatic isotopic equilibrium, have heavy δ18O values increasing from 6.3 ‰ in basaltic andesites to 7.1 ‰ in andesites, suggesting that magmatic evolution started from primary high-d18O basalt likely related to the abundant high-d18O sources described for Kamchatkan primitive magmas. The oxygen isotopic data support the conclusion that island-arc andesitic melts of Avachinsky Volcano generate predominantly due to the processes of fractional crystallization of high-d18O. The new data on composition of melt inclusions allowed us to reconstruct the entire spectrum of parental melts for Avacha volcano. Melt inclusions in different minerals form coherent trends of major elements, which can be well explained by fractional crystallization. Unlike some other island-arc volcanoes, Avachinskiy melts do not display clear bimodality of SiO2 content. Melts of intermediate compositions are relatively abundant and found in minerals from basaltic andesites. [1] Reuby & Blundy (2009) Nature, 461(7268), 1269-1273.

Measuring Solvent Content of Macromolecular Crystals Using Fluorescence Recovery after Photobleaching

NASA Astrophysics Data System (ADS)

Siewny, Matthew; Kmetko, Jan

2010-10-01

We work out a novel protocol for measuring the solvent content (the fraction of crystal volume occupied by solvent) in biological crystals by the technique of fluorescence recovery after photobleaching (FRAP). Crystals of proteins with widely varying known solvent content (lysozyme, thaumatin, catalase, and ferritin) were grown in their native solution doped with sodium fluorescein dye and hydroxylamine (to prevent dye from binding to amine groups of the proteins.) The crystals were irradiated by a broadband, high intensity light through knife slits, leaving a rectangular area of bleached dye within the crystals. Measuring the flow of dye out of the bleached area allowed us to construct a curve relating the diffusion coefficient of dye to the channel size within the crystals, by solving the diffusion equation analytically. This curve may be used to measure the solvent content of any biological crystal in its native solution and help determine the number of proteins in the crystallographic asymmetric unit cell in x-ray structure solving procedures.

Determining Kinetic Parameters for Isothermal Crystallization of Glasses

NASA Technical Reports Server (NTRS)

Ray, C. S.; Zhang, T.; Reis, S. T.; Brow, R. K.

2006-01-01

Non-isothermal crystallization techniques are frequently used to determine the kinetic parameters for crystallization in glasses. These techniques are experimentally simple and quick compared to the isothermal techniques. However, the analytical models used for non-isothermal data analysis, originally developed for describing isothermal transformation kinetics, are fundamentally flawed. The present paper describes a technique for determining the kinetic parameters for isothermal crystallization in glasses, which eliminates most of the common problems that generally make the studies of isothermal crystallization laborious and time consuming. In this technique, the volume fraction of glass that is crystallized as a function of time during an isothermal hold was determined using differential thermal analysis (DTA). The crystallization parameters for the lithium-disilicate (Li2O.2SiO2) model glass were first determined and compared to the same parameters determined by other techniques to establish the accuracy and usefulness of the present technique. This technique was then used to describe the crystallization kinetics of a complex Ca-Sr-Zn-silicate glass developed for sealing solid oxide fuel cells.

238U sbnd 230Th sbnd 226Ra disequilibria in young Mount St. Helens rocks: time constraint for magma formation and crystallization

NASA Astrophysics Data System (ADS)

Volpe, Alan M.; Hammond, Paul E.

1991-12-01

We use 238U-series nuclides and 230Th/ 232Th ratios measured by mass spectrometry to constrain processes and time scales of calc-alkaline magma genesis at Mount St. Helens, Washington. Olivine basalt, pyroxene andesites and dacites that erupted 10-2 ka ago show 3-14% ( 230Th) sbnd ( 238U) and 6-54% 226Ra sbnd 230Th disequilibria. Mineral phases exhibit robust ( 226Ra) sbnd ( 230Th) fractionation. Plagioclase has large 65-280% ( 226Ra) excesses, and magnetite has large 65% ( 226Ra) deficits relative to ( 230Th). Calculated partition coefficients for Ba, Th, and U in mineral-groundmass pairs, except Ba in plagioclase, are low (⩽ 0.04). Correlation between ( 226Ra/ 230Th ) activity ratios and rm/BaTh element ratios in the minerals suggests that 226Ra partitions similar to Ba during crystallization. Internal ( 230Th) sbnd ( 238U) isochrons for 1982 summit and East Dome dacites and Goat Rocks and Kalama andesites show that closed Th sbnd U system fractionation occurred 2-6 ka ago. Apparent internal isochrons for Castle Creek basalt (34 ka) and andesite (27 ka) suggest longer magma chamber residence times and mixing of old crystals and young melt. Mineral ( 226Ra) sbnd ( 230Th) disequilibrium on Ba-normalized internal isochron diagrams suggests average magma chamber residence times of 500-3000 years. In addition, radioactive ( 226Ra/ 230Th ) heterogeneity between minerals and groundmass or whole rock is evidence for open-system Ra sbnd Th behavior. This heterogeneity suggests there has been recent, post-crystallization, changes in melt chemical composition that affected 226Ra more than 230Th. Clearly, magma fractionation, residence and transport of crystal-melt before eruption of chemically diverse lavas at Mount St. Helens occurs over geologically short periods.

Rotational spectroscopy of cold and trapped molecular ions in the Lamb-Dicke regime

NASA Astrophysics Data System (ADS)

Alighanbari, S.; Hansen, M. G.; Korobov, V. I.; Schiller, S.

2018-06-01

Sympathetic cooling of trapped ions has been established as a powerful technique for the manipulation of non-laser-coolable ions1-4. For molecular ions, it promises vastly enhanced spectroscopic resolution and accuracy. However, this potential remains untapped so far, with the best resolution achieved being not better than 5 × 10-8 fractionally, due to residual Doppler broadening being present in ion clusters even at the lowest achievable translational temperatures5. Here we introduce a general and accessible approach that enables Doppler-free rotational spectroscopy. It makes use of the strong radial spatial confinement of molecular ions when trapped and crystallized in a linear quadrupole trap, providing the Lamb-Dicke regime for rotational transitions. We achieve a linewidth of 1 × 10-9 fractionally and 1.3 kHz absolute, an improvement of ≃50-fold over the previous highest resolution in rotational spectroscopy. As an application, we demonstrate the most precise test of ab initio molecular theory and the most accurate (1.3 × 10-9) determination of the proton mass using molecular spectroscopy. The results represent the long overdue extension of Doppler-free microwave spectroscopy of laser-cooled atomic ion clusters6 to higher spectroscopy frequencies and to molecules. This approach enables a wide range of high-accuracy measurements on molecules, both on rotational and, as we project, vibrational transitions.

Investigations of electromagnetic scattering by columnar ice crystals

NASA Technical Reports Server (NTRS)

Weil, H.; Senior, T. B. A.

1976-01-01

An integral equation approach was developed to determine the scattering and absorption of electromagnetic radiation by thin walled cylinders of arbitrary cross-section and refractive index. Based on this method, extensive numerical data was presented at infrared wavelengths for hollow hexagonal cross section cylinders which simulate columnar sheath ice crystals.

Sulfur-in-apatite: An indicator of the volatile evolution during lunar magmatism

NASA Astrophysics Data System (ADS)

Konecke, B.; Fiege, A.; Simon, A. C.; Holtz, F.

2017-12-01

The volatile content of lunar magmas remains controversial despite nearly five decades of interrogating samples from the NASA Apollo missions. Recently, the mineral apatite in lunar mare basalts has been investigated owing to its potential to constrain the volatile (F, Cl, H, S) budget of magmas [1-3]. The F-Cl-H signatures of lunar apatite were interpreted to record fractional crystallization, with nucleation and growth of apatite from a late-stage, interstitial, nearly anhydrous (<10 μg/g H2O), rhyolitic melt that evolved from a sulfide-undersaturated mare basalt [1]. The enigmatic S signature reported for those apatite grains was not interpreted due to the absence of published thermodynamic (partitioning) data for S. Here, we report new experimentally determined apatite/melt partition coefficients for S (DSap/m) at conditions applicable to lunar systems. The DSap/m values and thermodynamically modeled S content (XS) of lunar residual melt were used to constrain plausible S contents of lunar apatite produced by crystal fractionation (Sap = XS * DSap/m). Our results demonstrate that apatite crystallizing under lunar-like conditions from rhyolitic melt cannot obtain the reported 430 μg/g of S [2] by fractional crystallization. The results indicate that 5-35x higher S contents than feasible in sulfide-undersaturated, hydrous and dry rhyolitic melt, respectively, would be required to support crystal fractionation models [1]. Even elevated water concentrations in a sulfide-saturated rhyolitic melt cannot explain the S contents of lunar apatite rims. We propose two plausible scenarios: (A) The necessary concentration of S in rhyolitic melts may be achieved at >5 orders of magnitude higher fO2 (>ΔFMQ+1.2) than reported for lunar magmas, where S6+ is the prevalent oxidation state of S in rhyolitic melt, related to the significant degassing and preferential loss of H2 that drives oxidation of the residual melt [4]. (B) The volatile (F-Cl-H-S) signatures of lunar apatites may reflect cryptic metasomatic reactions between apatite and a S-Cl-rich, F-poor volatile phase released by underlying magma reservoirs. [1] Boyce et at., 2014, Science 344:400-402. [2] Greenwood et al., 2011, Nat. Geosci 4:79-82. [3] Webster et al., 2009, Geochim. Cosmochim. Acta 73, 559-581. [4] McCanta et al., 2017, Icarus 285, 95-102.

The Axum-Adwa basalt-trachyte complex: a late magmatic activity at the periphery of the Afar plume

NASA Astrophysics Data System (ADS)

Natali, C.; Beccaluva, L.; Bianchini, G.; Siena, F.

2013-08-01

The Axum-Adwa igneous complex consists of a basalt-trachyte (syenite) suite emplaced at the northern periphery of the Ethiopian plateau, after the paroxysmal eruption of the Oligocene (ca 30 Ma) continental flood basalts (CFB), which is related to the Afar plume activity. 40Ar/39Ar and K-Ar ages, carried out for the first time on felsic and basaltic rocks, constrain the magmatic age of the greater part of the complex around Axum to 19-15 Ma, whereas trachytic lavas from volcanic centres NE of Adwa are dated ca 27 Ma. The felsic compositions straddle the critical SiO2-saturation boundary, ranging from normative quartz trachyte lavas east of Adwa to normative (and modal) nepheline syenite subvolcanic domes (the obelisks stones of ancient axumites) around Axum. Petrogenetic modelling based on rock chemical data and phase equilibria calculations by PELE (Boudreau 1999) shows that low-pressure fractional crystallization processes, starting from mildly alkaline- and alkaline basalts comparable to those present in the complex, could generate SiO2-saturated trachytes and SiO2-undersaturated syenites, respectively, which correspond to residual liquid fractions of 17 and 10 %. The observed differentiation processes are consistent with the development of rifting events and formation of shallow magma chambers plausibly located between displaced (tilted) crustal blocks that favoured trapping of basaltic parental magmas and their fractionation to felsic differentiates. In syenitic domes, late- to post-magmatic processes are sometimes evidenced by secondary mineral associations (e.g. Bete Giorgis dome) which overprint the magmatic parageneses, and mainly induce additional nepheline and sodic pyroxene neo-crystallization. These metasomatic reactions were promoted by the circulation of Na-Cl-rich deuteric fluids (600-400 °C), as indicated by mineral and bulk rock chemical budgets as well as by δ18O analyses on mineral separates. The occurrence of this magmatism post-dating the CFB event, characterized by comparatively lower volume of more alkaline products, conforms to the progressive vanishing of the Afar plume thermal effects and the parallel decrease of the partial melting degrees of the related mantle sources. This evolution is also concomitant with the variation of the tectono-magmatic regime from regional lithospheric extension (CFB eruption) to localized rifting processes that favoured magmatic differentiation.

Effective Method of Purification of Betulin from Birch Bark: The Importance of Its Purity for Scientific and Medicinal Use

PubMed Central

Šiman, Pavel; Filipová, Alžběta; Tichá, Alena; Niang, Mohamed; Bezrouk, Aleš; Havelek, Radim

2016-01-01

A new and relatively simple method for purification of betulin from birch bark extract was developed in this study. Its five purification steps are based on the differential solubility of extract components in various solvents and their crystallization and/or precipitation, on their affinity for Ca(OH)2 in ethanol, and on the affinity of some impurities for silica gel in chloroform. In addition, all used solvents can be simply recycled. Betulin of more than 99% purity can be prepared by this method with minimal costs. Various observations including crystallization of betulin, changes in crystals during heating, and attempt of localization of betulin in outer birch bark are also described in this work. The original extract, fraction without betulinic acid and lupeol, amorphous fraction of pure betulin, final crystalline fraction of pure betulin and commercial betulin as a standard were employed to determine the antiproliferative/cytotoxic effect. We used WST-1 tetrazolium-based assays with triple negative breast cancer cell line BT-549. The decrease in cell survival showed clear relationship with the purity of the samples, being most pronounced using our final product of pure crystalline betulin. WST-1 proliferation/cytotoxicity test using triple negative breast cancer cell line BT-549 clearly showed the importance of purity of betulin for biological experiments and, apparently, for its medicinal use. PMID:27152419

The connection between crustal reworking and petrological diversity in the deep crust: clues from migmatites

NASA Astrophysics Data System (ADS)

Carvalho, Bruna B.; Sawyer, Edward W.; de Assis Janasi, Valdecir

2016-04-01

The deep levels of the continental crust have been extensively reworked as result of crustal differentiation. Migmatites are widespread in these high-grade metamorphic terrains, and provide valuable information on how processes such as partial melting, segregation of the melt from the residue and subsequent chemical exchanges lead to the petrological diversity found in the deep crust. This study investigates processes that transformed a largely uniform, metagranodiorite protolith into a very complex migmatite that contains three varieties of diatexites (grey, schlieren and homogenous diatexites) and several types of leucosomes. The Kinawa Migmatite is part of the Archean TTG crust in the São Francisco Craton (Brazil), which has been reworked in a shear zone environment at upper amphibolite facies conditions (<730°C and 5-6 kbar); thus it may be typical of crustal reworking in the interior of old cratons [1]. Grey diatexites are residual rocks formed by the extraction of a water-fluxed melt created via the reaction Pl + Kfs + Qz + H2O = melt. Diversity within the grey diatexites arises from different degrees of melt segregation (maximum ~40% melt). Schlieren diatexites are very heterogeneous rocks in which residuum-rich domains alternate with leucocratic quartzo-feldspathic domains where melt accumulated. Homogeneous diatexites are coarse-grained leucocratic rocks and represent larger bodies of anatectic melt with minor amounts (<20%) of entrained residuum. Leucosomes display a wide range of compositions from tonalitic to alkali-feldspar granite. Leucosomes, homogeneous diatexites and the quartzo-feldspathic domains in the schlieren diatexites all show a sequence of microstructural stages from plagioclase-dominated to K-feldspar-dominated frameworks many of which show evidence for tectonic compaction. Thus, further segregation of melt from solids occurred during crystallization. Minor amphibolite dykes in the metagranodiorite did not melt. They occur as angular to rounded fragments (schollen or rafts) in the diatexites and show strong evidence for mechanical and chemical interaction with their melt rich hosts. Typically, the diatexites and the leucosomes around the schollen contain higher proportion of amphibole and/or biotite than that farther away; a number of features suggest that this is due to disaggregation that contaminated the melt rich rocks. Our data indicates that in the deep levels of the crust petrological diversity is produced by melt segregation, both during partial melting and crystallization, and by interaction of the anatectic melt with unmelted material in the source. During melting, segregation produced residuum plus anatectic melt and all intermediate stages, whereas during crystallization it resulted in crystal fractionation and generated diverse plagioclase-rich rocks and fractionated melts. Finally, crystals disaggregated from the amphibolites entrained and interact with anatectic melt producing leucosomes and diatexites with the compositional signature of contamination. [1] Carvalho, B.B; Sawyer, E.W.; Janasi, V.A. (2016). Crustal reworking in a shear zone: transformation of metagranite to migmatite. Journal of Metamorphic Geology DOI: 10.1111/jmg.12180

Transport phenomena in the crystallization of lysozyme by osmotic dewatering and liquid-liquid diffusion in low gravity

NASA Technical Reports Server (NTRS)

Todd, Paul; Sportiello, Michael G.; Gregory, Derek; Cassanto, John M.; Alvarado, Ulises A.; Ostroff, Robert; Korszun, Z. R.

1993-01-01

Two methods of protein crystallization, osmotic dewatering and liquid-liquid diffusion, like the vapor diffusion (hanging-drop and sessile-drop) methods allow a gradual approach to supersaturation conditions. The crystallization of hen egg-white lysozyme, an extensively characterized protein crystal, in the presence of sodium chloride was used as an experimental model with which to compare these two methods in low gravity and in the laboratory. Comparisons of crystal growth rates by the two methods under the two conditions have, to date, indicated that the rate of crystal growth by osmotic dewatering is nearly the same in low gravity and on the ground, while much faster crystal growth rates can be achieved by the liquid-liquid diffusion method in low gravity.

Piezoelectric single crystals for ultrasonic transducers in biomedical applications

PubMed Central

Zhou, Qifa; Lam, Kwok Ho; Zheng, Hairong; Qiu, Weibao; Shung, K. Kirk

2014-01-01

Piezoelectric single crystals, which have excellent piezoelectric properties, have extensively been employed for various sensors and actuators applications. In this paper, the state–of–art in piezoelectric single crystals for ultrasonic transducer applications is reviewed. Firstly, the basic principles and design considerations of piezoelectric ultrasonic transducers will be addressed. Then, the popular piezoelectric single crystals used for ultrasonic transducer applications, including LiNbO3 (LN), PMN–PT and PIN–PMN–PT, will be introduced. After describing the preparation and performance of the single crystals, the recent development of both the single–element and array transducers fabricated using the single crystals will be presented. Finally, various biomedical applications including eye imaging, intravascular imaging, blood flow measurement, photoacoustic imaging, and microbeam applications of the single crystal transducers will be discussed. PMID:25386032

Petrology, geochemistry and LA-ICP-MS U-Pb geochronology of Paleoproterozoic basement rocks in Bangladesh: An evaluation of calc-alkaline magmatism and implication for Columbia supercontinent amalgamation

NASA Astrophysics Data System (ADS)

Hossain, Ismail; Tsunogae, Toshiaki; Tsutsumi, Yukiyasu; Takahashi, Kazuki

2018-05-01

The Paleoproterozoic (1.7 Ga) basement rocks from Maddhapara, Bangladesh show a large range of chemical variations (e.g. SiO2 = 50.7-74.7%) and include diorite, quartz diorite, monzodiorite, quartz monzonite and granite. The pluton overall displays metaluminous, calc-alkaline orogenic suite; mostly I-type suites formed within subduction-related magmatism. The observed major elements show general trends for fractional crystallization. Trace element contents also indicate the possibility of a fractionation or assimilation; explain the entire variation from diorite to monzonite, even granite. The pluton may have evolved the unique chemical features by a process that included partial melting of calc-alkaline lithologies and mixing of mantle-derived magmas, followed by fractional crystallization, and by assimilation of country rocks. The pluton shows evidence of crystal fractionation involving largely plagioclase, amphibole and possibly biotite. Some of the fractionated magmas may have mixed with more potassic melts from distinct parts of the continental lithosphere to produce granites and/or pegmatites. New geochronological results of granitic pegmatite (1722 ± 10 Ma) are indisputably consistent with diorite and tonalite and those data showing credible geochronological sequence (i.e., diorite - tonalite - granitic pegmatite). Identical Paleoproterozoic age (1.7 Ga) with distinctive magmatism of the Maddhapara basement rocks have agreeable relationship with the CITZ, India. The consistent magmatism is also common in the Transamazonian of South America, Trans-Hudson orogeny in North America, Bohemian Massif and the Svecofennian, Poland, have identified the sequential growth of the continent through the amalgamation of juvenile terrains, succeeded by a major collisional orogeny. Such Paleoproterozoic subduction-related orogens in Australia have similar counterparts in Antarctica and other part of the world. These types of Paleoproterozoic magmatism dominantly contributed to assemble, amalgamation and breakup of the enormous Columbia supercontinent.

Calcium Isotopic Compositions of Normal Mid-Ocean Ridge Basalts From the Southern Juan de Fuca Ridge

NASA Astrophysics Data System (ADS)

Zhu, Hongli; Liu, Fang; Li, Xin; Wang, Guiqin; Zhang, Zhaofeng; Sun, Weidong

2018-02-01

Mantle peridotites show that Ca is isotopically heterogeneous in Earth's mantle, but the mechanism for such heterogeneity remains obscure. To investigate the effect of partial melting on Ca isotopic fractionation and the mechanism for Ca isotopic heterogeneity in the mantle, we report high-precision Ca isotopic compositions of the normal Mid-Ocean Ridge Basalts (N-MORB) from the southern Juan de Fuca Ridge. δ44/40Ca of these N-MORB samples display a small variation ranging from 0.75 ± 0.05 to 0.86 ± 0.03‰ (relative to NIST SRM 915a, a standard reference material produced by the National Institute of Standards and Technology), which are slightly lower than the estimated Upper Mantle value of 1.05 ± 0.04‰ and the Bulk Silicate Earth (BSE) value of 0.94 ± 0.05‰. This phenomenon cannot be explained by fractional crystallization, because olivine and orthopyroxene fractional crystallization has limited influence on δ44/40Ca of N-MORB due to their low CaO contents, while plagioclase fractional crystallization cannot lead to light Ca isotopic compositions of the residue magma. Instead, the lower δ44/40Ca of N-MORB samples compared to their mantle source is most likely caused by partial melting. The offset in δ44/40Ca between N-MORB and BSE indicates that at least 0.1-0.2‰ fractionation would occur during partial melting and light Ca isotopes are preferred to be enriched in magma melt, which is in accordance with the fact that δ44/40Ca of melt-depleted peridotites are higher than fertile peridotites in literature. Therefore, partial melting is an important process that can decrease δ44/40Ca in basalts and induce Ca isotopic heterogeneity in Earth's mantle.

Petrogenesis of the Late Triassic diorites in the Hoh Xil area, northern Tibet: Insights into the origin of the high-Mg# andesitic signature of continental crust

NASA Astrophysics Data System (ADS)

Wang, Jun; Gou, Guo-Ning; Wang, Qiang; Zhang, Chunfu; Dan, Wei; Wyman, Derek A.; Zhang, Xiu-Zheng

2018-02-01

An integrated petrologic, geochronologic, major and trace element geochemical, and Sr-Nd-Hf isotopic study of Late Triassic ( 215 Ma) diorites from the Hoh Xil area, northern Tibet, provides new constraints on the genesis of intermediate magmas and insights into the origin of the high-Mg# andesitic signature of continental crust. These dioritic rocks are characterized by high MgO contents (3.3-5.0 wt%) and Mg# values (50-57) comparable to the estimates for the bulk continental crust at the same level of SiO2 contents (61.1-64.5 wt%). They also display continental crust-like trace element distribution patterns and uniformly enriched isotope compositions ([87Sr/86Sr]i = 0.7081 to 0.7094, ɛNd[t] = - 8.0 to - 6.9, and ɛHf[t]zircon = - 10.1 to - 5.0). Combining our results with published data from crystallization experiments, we propose that they were probably produced by fractional crystallization from a primitive andesite parent, rather than a primitive basalt parent. This parental magma may be geochemically similar to the roughly contemporaneous primitive andesites in the adjacent Malanshan area of northern Tibet. Our compilation of modern arc lavas shows that progressive fractional crystallization of primitive andesites is also required to reproduce the Mg# versus SiO2 array for natural arc magmas, in addition to differentiation of mantle-derived primitive basaltic magmas and/or mixing of basaltic with felsic magmas. Therefore, we emphasize that fractional crystallization of primitive andesitic magmas is potentially a frequent occurrence in arc crust and hence may play an important role in producing the high-Mg# signature of intermediate magmas comprising the continental crust.

Red Sea rift-related Quseir basalts, central Eastern Desert, Egypt: Petrogenesis and tectonic processes

NASA Astrophysics Data System (ADS)

Farahat, Esam S.; Ali, Shehata; Hauzenberger, Christoph

2017-01-01

Mineral and whole-rock chemistry of Red Sea rift-related Tertiary basalts from south Quseir city, central Eastern Desert of Egypt is presented to investigate their petrogenesis and relationship to tectonic processes. The south Quseir basalts (SQB) are classified as high-Ti (TiO2 >2 wt.%) subalkaline transitional lava emplaced in an anorogenic tectonic setting. Their Mg# varies from 48 to 53 indicating the evolved nature of the SQB. Pearce element ratios suggest that the SQB magmas evolved via fractional crystallization of olivine + clinopyroxene ± plagioclase, but the absence of Eu anomalies argues against significant plagioclase fractionation. Clinopyroxene compositions provide evidence for polybaric fractionation of the parental mafic magmas. Estimated temperatures of crystallization are 1015 to 1207 °C for clinopyroxene and 1076 to 1155 °C for plagioclase. These values are interpreted to result from early stage crystallization of clinopyroxene followed by concurrent crystallization of clinopyroxene and plagioclase. The incompatible trace element signatures of the SQB (La/Ba = 0.08-0.10 and La/Nb = 0.89-1.04) are comparable to those of ocean island basalts (OIB) generated from an asthenospheric mantle source unaffected by subduction components. Modeling calculations indicate that the SQB primary magmas were derived from 4-5% partial melting of a garnet-bearing lherzolite mantle source. The NE Egyptian basaltic volcanism is spatially and temporally related to Red Sea rifting and to the local E-W striking faults, confirming a relationship to tectonic activity. Our results suggest that the extensional regime associated with Red Sea rifting controlled the generation of the Egyptian basalts, likely as a result of passive upwelling of asthenospheric mantle.

Design and performance evaluation of a high resolution IRI-microPET preclinical scanner

NASA Astrophysics Data System (ADS)

Islami rad, S. Z.; Peyvandi, R. Gholipour; lehdarboni, M. Askari; Ghafari, A. A.

2015-05-01

PET for small animal, IRI-microPET, was designed and built at the NSTRI. The scanner is made of four detectors positioned on a rotating gantry at a distance 50 mm from the center. Each detector consists of a 10×10 crystal matrix of 2×2×10 mm3 directly coupled to a PS-PMT. A position encoding circuit for specific PS-PMT has been designed, built and tested with a PD-MFS-2MS/s-8/14 data acquisition board. After implementing reconstruction algorithms (FBP, MLEM and SART) on sinograms, images quality and system performance were evaluated by energy resolution, timing resolution, spatial resolution, scatter fraction, sensitivity, RMS contrast and SNR parameters. The energy spectra were obtained for the crystals with an energy window of 300-700 keV. The energy resolution in 511 keV averaged over all modules, detectors, and crystals, was 23.5%. A timing resolution of 2.4 ns FWHM obtained by coincidence timing spectrum was measured with crystal LYSO. The radial and tangential resolutions for 18F (1.15-mm inner diameter) at the center of the field of view were 1.81 mm and 1.90 mm, respectively. At a radial offset of 5 mm, the FWHM values were 1.96 and 2.06 mm. The system scatter fraction was 7.1% for the mouse phantom. The sensitivity was measured for different energy windows, leading to a sensitivity of 1.74% at the center of FOV. Also, images quality was evaluated by RMS contrast and SNR factors, and the results show that the reconstructed images by MLEM algorithm have the best RMS contrast, and SNR. The IRI-microPET presents high image resolution, low scatter fraction values and improved SNR for animal studies.

Flight Experiments of Physical Vapor Transport of ZnSe: Growth of Crystals in Various Convective Conditions

NASA Technical Reports Server (NTRS)

Su, Ching-Hua

2015-01-01

A low gravity material experiment will be performed in the Material Science Research Rack (MSRR) on International Space Station (ISS). The flight experiment will conduct crystal growths of ZnSe and related ternary compounds, such as ZnSeS and ZnSeTe, by physical vapor transport (PVT). The main objective of the project is to determine the relative contributions of gravity-driven fluid flows to the compositional distribution, incorporation of impurities and defects, and deviation from stoichiometry observed in the grown crystals as results of buoyancy-driven convection and growth interface fluctuations caused by irregular fluid-flows on Earth. The investigation consists of extensive ground-based experimental and theoretical research efforts and concurrent flight experimentation. The objectives of the ground-based studies are (1) obtain the experimental data and conduct the analyses required to define the optimum growth parameters for the flight experiments, (2) perfect various characterization techniques to establish the standard procedure for material characterization, (3) quantitatively establish the characteristics of the crystals grown on Earth as a basis for subsequent comparative evaluations of the crystals grown in a low-gravity environment and (4) develop theoretical and analytical methods required for such evaluations. ZnSe and related ternary compounds have been grown by vapor transport technique with real time in-situ non-invasive monitoring techniques. The grown crystals have been characterized extensively by various techniques to correlate the grown crystal properties with the growth conditions. This talk will focus on the ground-based studies on the PVT crystal growth of ZnSe and related ternary compounds, especially the effects of different growth orientations related to gravity direction on the grown crystals.

Extending the applicability of the Goldschmidt tolerance factor to arbitrary ionic compounds

PubMed Central

Sato, Toyoto; Takagi, Shigeyuki; Deledda, Stefano; Hauback, Bjørn C.; Orimo, Shin-ichi

2016-01-01

Crystal structure determination is essential for characterizing materials and their properties, and can be facilitated by various tools and indicators. For instance, the Goldschmidt tolerance factor (T) for perovskite compounds is acknowledged for evaluating crystal structures in terms of the ionic packing. However, its applicability is limited to perovskite compounds. Here, we report on extending the applicability of T to ionic compounds with arbitrary ionic arrangements and compositions. By focussing on the occupancy of constituent spherical ions in the crystal structure, we define the ionic filling fraction (IFF), which is obtained from the volumes of crystal structure and constituent ions. Ionic compounds, including perovskites, are arranged linearly by the IFF, providing consistent results with T. The linearity guides towards finding suitable unit cell and composition, thus tackling the main obstacle for determining new crystal structures. We demonstrate the utility of the IFF by solving the structure of three hydrides with new crystal structures. PMID:27032978

Extending the applicability of the Goldschmidt tolerance factor to arbitrary ionic compounds.

PubMed

Sato, Toyoto; Takagi, Shigeyuki; Deledda, Stefano; Hauback, Bjørn C; Orimo, Shin-ichi

2016-04-01

Crystal structure determination is essential for characterizing materials and their properties, and can be facilitated by various tools and indicators. For instance, the Goldschmidt tolerance factor (T) for perovskite compounds is acknowledged for evaluating crystal structures in terms of the ionic packing. However, its applicability is limited to perovskite compounds. Here, we report on extending the applicability of T to ionic compounds with arbitrary ionic arrangements and compositions. By focussing on the occupancy of constituent spherical ions in the crystal structure, we define the ionic filling fraction (IFF), which is obtained from the volumes of crystal structure and constituent ions. Ionic compounds, including perovskites, are arranged linearly by the IFF, providing consistent results with T. The linearity guides towards finding suitable unit cell and composition, thus tackling the main obstacle for determining new crystal structures. We demonstrate the utility of the IFF by solving the structure of three hydrides with new crystal structures.

An expanded model and application of the combined effect of crystal-size distribution and crystal shape on the relative viscosity of magmas

NASA Astrophysics Data System (ADS)

Klein, Johannes; Mueller, Sebastian P.; Helo, Christoph; Schweitzer, Silja; Gurioli, Lucia; Castro, Jonathan M.

2018-05-01

This study examines the combined effect of crystal-size distributions (CSD) and crystal shape on the rheology of vesicle free magmatic suspensions and provides the first practical application of an empirical model to estimate the relative effect of crystal content and CSD's on the viscosity of magma directly from textural image analysis of natural rock samples in the form of a user-friendly texture-rheology spreadsheet calculator. We extend and apply established relationships between the maximum packing fraction ϕm of a crystal bearing suspension and both its rheological properties and the polydispersity γ of a CSD. By using analogue rotational rheometric experiments with glass fibres and glass flakes in silicone oil acting as magma equivalent, this study also provides new insights in the relationship between ϕm and the aspect ratio rp of suspended particles.

Synthesis and Characterization of Functional Mesostructures Using Colloidal Crystal Templating

DTIC Science & Technology

2004-01-01

fluorescent probes in aqueous polymer solutions . Khoury and co-workers measured the diffusion coefficient of several fluorescein-labeled proteins in...diffraction naq refractive index of the aqueous solution phase xvii ni refractive index of component i ngel refractive index of the hydrogel...phase Tg glass transition temperature α angle of diffraction φaq volume fraction of the aqueous solution phase φi volume fraction of

Platinum-group element, Gold, Silver and Base Metal distribution in compositionally zoned sulfide droplets from the Medvezky Creek Mine, Noril'sk, Russia

USGS Publications Warehouse

Barnes, S.-J.; Cox, R.A.; Zientek, M.L.

2006-01-01

Concentrations of Ag, Au, Cd, Co, Re, Zn and Platinum-group elements (PGE) have been determined in sulfide minerals from zoned sulfide droplets of the Noril'sk 1 Medvezky Creek Mine. The aims of the study were; to establish whether these elements are located in the major sulfide minerals (pentlandite, pyrrhotite, chalcopyrite and cubanite), to establish whether the elements show a preference for a particular sulfide mineral and to investigate the model, which suggests that the zonation in the droplets is caused by the crystal fractionation of monosulfide solid solution (mss). Nickel, Cu, Ag, Re, Os, Ir, Ru, Rh and Pd, were found to be largely located in the major sulfide minerals. In contrast, less than 25% of the Au, Cd, Pt and Zn in the rock was found to be present in these sulfides. Osmium, Ir, Ru, Rh and Re were found to be concentrated in pyrrhotite and pentlandite. Palladium and Co was found to be concentrated in pentlandite. Silver, Cd and Zn concentrations are highest in chalcopyrite and cubanite. Gold and platinum showed no preference for any of the major sulfide minerals. The enrichment of Os, Ir, Ru, Rh and Re in pyrrhotite and pentlandite (exsolution products of mss) and the low levels of these elements in the cubanite and chalcopyrite (exsolution products of intermediate solid solution, iss) support the mss crystal fractionation model, because Os, Ir, Ru, Rh and Re are compatible with mss. The enrichment of Ag, Cd and Zn in chalcopyrite and cubanite also supports the mss fractionation model these minerals are derived from the fractionated liquid and these elements are incompatible with mss and thus should be enriched in the fractionated liquid. Gold and Pt do not partition into either iss or mss and become sufficiently enriched in the final fractionated liquid to crystallize among the iss and mss grains as tellurides, bismithides and alloys. During pentlandite exsolution Pd appears to have diffused from the Cu-rich portion of the droplet into pentlandite. ?? Springer-Verlag 2006.

Zinc and volatile element loss during planetary magma ocean phases

NASA Astrophysics Data System (ADS)

Dhaliwal, Jasmeet K.; Day, James M. D.; Moynier, Frédéric

2016-10-01

Zinc is a moderately volatile element and a key tracer of volatile depletion on planetary bodies due to lack of significant isotopic fractionation under high-temperature processes. Terrestrial basalts have δ66Zn values similar to some chondrites (+ 0.15 to 0.3‰ where [{66Zn/64Znsample/66Zn/64ZnJMC-Lyon-1} × 1000]) and elevated Zn concentrations (100 ppm). Lunar mare basalts yield a mean δ66Zn value of +1.4 ± 0.5‰ and have low Zn concentrations (~2 ppm). Late-stage lunar magmatic products, such as ferroan anorthosite, Mg-suite and Alkali suite rocks exhibit heavier δ66Zn values (+3 to +6‰). The heavy δ66Zn lunar signature is thought to reflect evaporative loss and fractionation of zinc, either during a giant impact or in a magma ocean phase.We explore conditions of volatile element loss within a lunar magma ocean (LMO) using models of Zn isotopic fractionation that are widely applicable to planetary magma oceans. For the Moon, our objective was to identify conditions that would yield a δ66Zn signature of ~ +1.4‰ within the mantle, assuming a terrestrial mantle zinc starting composition.We examine two cases of zinc evaporative fractionation: (1) lunar surface zinc fractionation that was completed prior to LMO crystallization and (2) lunar surface zinc fractionation that was concurrent with LMO crystallization. The first case resulted in a homogeneous lunar mantle and the second case yielded a stratified lunar mantle, with the greatest zinc isotopic enrichment in late-stage crystallization products. This latter case reproduces the distribution of zinc isotope compositions in lunar materials quite well.We find that hydrodynamic escape was not a dominant process in losing Zn, but that erosion of a nascent lunar atmosphere, or separation of condensates into a proto-lunar crust are possible. While lunar volatile depletion is still possible as a consequence of the giant impact, this process cannot reproduce the variable δ66Zn found in the Moon. Outgassing during magma ocean phases would have led to volatile-depleted planetesimal feed-stocks that would have profoundly affected the ultimate volatile inventories of larger planetary bodies.

The stable Cr isotopic compositions of chondrites and silicate planetary reservoirs

NASA Astrophysics Data System (ADS)

Schoenberg, Ronny; Merdian, Alexandra; Holmden, Chris; Kleinhanns, Ilka C.; Haßler, Kathrin; Wille, Martin; Reitter, Elmar

2016-06-01

The depletion of chromium in Earth's mantle (∼2700 ppm) in comparison to chondrites (∼4400 ppm) indicates significant incorporation of chromium into the core during our planet's metal-silicate differentiation, assuming that there was no significant escape of the moderately volatile element chromium during the accretionary phase of Earth. Stable Cr isotope compositions - expressed as the ‰-difference in 53Cr/52Cr from the terrestrial reference material SRM979 (δ53/52CrSRM979 values) - of planetary silicate reservoirs might thus yield information about the conditions of planetary metal segregation processes when compared to chondrites. The stable Cr isotopic compositions of 7 carbonaceous chondrites, 11 ordinary chondrites, 5 HED achondrites and 2 martian meteorites determined by a double spike MC-ICP-MS method are within uncertainties indistinguishable from each other and from the previously determined δ53/52CrSRM979 value of -0.124 ± 0.101‰ for the igneous silicate Earth. Extensive quality tests support the accuracy of the stable Cr isotope determinations of various meteorites and terrestrial silicates reported here. The uniformity in stable Cr isotope compositions of samples from planetary silicate mantles and undifferentiated meteorites indicates that metal-silicate differentiation of Earth, Mars and the HED parent body did not cause measurable stable Cr isotope fractionation between these two reservoirs. Our results also imply that the accretionary disc, at least in the inner solar system, was homogeneous in its stable Cr isotopic composition and that potential volatility loss of chromium during accretion of the terrestrial planets was not accompanied by measurable stable isotopic fractionation. Small but reproducible variations in δ53/52CrSRM979 values of terrestrial magmatic rocks point to natural stable Cr isotope variations within Earth's silicate reservoirs. Further and more detailed studies are required to investigate whether silicate differentiation processes, such as partial mantle melting and crystal fractionation, can cause stable Cr isotopic fractionation on Earth and other planetary bodies.

Berkeley Screen: a set of 96 solutions for general macromolecular crystallization

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

Pereira, Jose H.; McAndrew, Ryan P.; Tomaleri, Giovani P.

Using statistical analysis of the Biological Macromolecular Crystallization Database, combined with previous knowledge about crystallization reagents, a crystallization screen called the Berkeley Screen has been created. Correlating crystallization conditions and high-resolution protein structures, it is possible to better understand the influence that a particular solution has on protein crystal formation. Ions and small molecules such as buffers and precipitants used in crystallization experiments were identified in electron density maps, highlighting the role of these chemicals in protein crystal packing. The Berkeley Screen has been extensively used to crystallize target proteins from the Joint BioEnergy Institute and the Collaborative Crystallography programmore » at the Berkeley Center for Structural Biology, contributing to several Protein Data Bank entries and related publications. The Berkeley Screen provides the crystallographic community with an efficient set of solutions for general macromolecular crystallization trials, offering a valuable alternative to the existing commercially available screens. The Berkeley Screen provides an efficient set of solutions for general macromolecular crystallization trials.« less

Berkeley Screen: a set of 96 solutions for general macromolecular crystallization

DOE PAGES

Pereira, Jose H.; McAndrew, Ryan P.; Tomaleri, Giovani P.; ...

2017-09-05

Using statistical analysis of the Biological Macromolecular Crystallization Database, combined with previous knowledge about crystallization reagents, a crystallization screen called the Berkeley Screen has been created. Correlating crystallization conditions and high-resolution protein structures, it is possible to better understand the influence that a particular solution has on protein crystal formation. Ions and small molecules such as buffers and precipitants used in crystallization experiments were identified in electron density maps, highlighting the role of these chemicals in protein crystal packing. The Berkeley Screen has been extensively used to crystallize target proteins from the Joint BioEnergy Institute and the Collaborative Crystallography programmore » at the Berkeley Center for Structural Biology, contributing to several Protein Data Bank entries and related publications. The Berkeley Screen provides the crystallographic community with an efficient set of solutions for general macromolecular crystallization trials, offering a valuable alternative to the existing commercially available screens. The Berkeley Screen provides an efficient set of solutions for general macromolecular crystallization trials.« less

Experiment 3: Zeolite Crystal Growth in Microgravity- The USML-2 Mission

NASA Technical Reports Server (NTRS)

Bac, Nurcan; Warzywoda, Juliusz; Sacco, Albert, Jr.

1998-01-01

The extensive use of zeolites and their impact on the world's economy leads to many efforts to characterize their structure, and to improve the knowledge base for nucleation and growth of these crystals. The Zeolite Crystal Growth (ZCG) experiment on USML-2 aims to enhance the understanding of nucleation and growth of zeolite crystals while attempting to provide a means of controlling the defect concentration in microgravity. Zeolites A, X, Beta, and Silicalite were grown during the 16-day USML-2 mission. The solutions where the nucleation event was controlled yielded larger and more uniform crystals of better morphology and purity than their terrestrial/control counterparts. Space-grown Beta crystals were free of line defects while terrestrial/controls had substantial defects.

Oligonucleotide flexibility dictates crystal quality in DNA-programmable nanoparticle superlattices.

PubMed

Senesi, Andrew J; Eichelsdoerfer, Daniel J; Brown, Keith A; Lee, Byeongdu; Auyeung, Evelyn; Choi, Chung Hang J; Macfarlane, Robert J; Young, Kaylie L; Mirkin, Chad A

2014-11-12

The evolution of crystallite size and microstrain in DNA-mediated nanoparticle superlattices is dictated by annealing temperature and the flexibility of the interparticle bonds. This work addresses a major challenge in synthesizing optical metamaterials based upon noble metal nanoparticles by enabling the crystallization of large nanoparticles (100 nm diameter) at high volume fractions (34% metal). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Flight evidence of spacecraft surface contamination rate enhancement by spacecraft charging obtained with a quartz crystal microbalance

NASA Technical Reports Server (NTRS)

Clark, D. M.; Hall, D. F.

1980-01-01

The significance of the fraction of the mass outgassed by a negatively charged space vehicle which is ionized within the vehicle plasma sheath and electrostatically reattracted to the space vehicle was determined. The ML-12 retarding potential analyzer/temperature controlled quartz crystal microbalances (RPA/TQCMs) distinguishes between charged and neutral molecules and investigates contamination mass transport mechanism. Two long term, quick look flight data sets indicate that on the average a significant fraction of mass arriving at one RPA/TQCM is ionized. It is assumed that vehicle frame charging during these periods was approximately uniformly distributed in degree and frequency. It is shown that electrostatic reattraction of ionized molecules is an important contamination mechanism at and near geosynchronous altitudes.

Convoy electron emission from resonant coherently excited 390 MeV/u hydrogen-like Ar ions

NASA Astrophysics Data System (ADS)

Azuma, T.; Takabayashi, Y.; Ito, T.; Komaki, K.; Yamazaki, Y.; Takada, E.; Murakami, T.

2003-12-01

Energetic ions traveling through a single crystal are excited by an oscillating crystal field produced by a periodic arrangement of the atomic strings/planes, which is called Resonant Coherent Excitation (RCE). We have observed enhancement of convoy electron yields associated with RCE of 1s electron to the n=2 excited states of 390 MeV/u hydrogen-like Ar 17+ ions passing through a Si crystal in the (2 2¯ 0) planar channeling condition. Lost electrons from projectile ions due to ionization contribute to convoy electrons emitted in the forward direction with the same velocity as the projectile ions. With combination of a magnet and a thick Si solid-state detector, we measured the energy spectra of convoy electrons of about 200 keV emitted at 0°. The convoy electron yield as a function of the transition energy, i.e. the resonance profile, has a similar structure to the resonance profile observed through the ionized fraction of the emerging ions. It is explained by the fact that both enhancements are due to increase in the fraction of the excited states from which electrons are more easily ionized by target electron impact in the crystal than from the ground state.

Evidence for hydrous high-MgO melts in the Precambrian

NASA Astrophysics Data System (ADS)

Stone, William E.; Deloule, Etienne; Larson, Michelle S.; Lesher, C. Michael

1997-02-01

Prevailing petrogenetic models for Precambrian high-MgO melts such as komatiites invoke crystallization from nearly anhydrous melts (≪0.5% H2O) generated by partial melting of mantle peridotite at temperatures of (≤ 1900 °C and pressures of (18 GPa. However, ultramafic cumulate and gabbro zones of komatiitic and other high-MgO units in Precambrian greenstone belts contain vesicles and minor to major amounts (≤ 25%) of igneous amphibole. The textures (oikocrysts, rims on intercumulate pyroxene, and mineral inclusions within orthocumulate olivine) and the water-rich compositions (1.00% 2.50% H2O) of igneous amphiboles from the Archean Abitibi belt indicate crystallization in situ from significantly hydrous melts while the melt fraction was still as high as 40% 50%. Comparisons to experimental phase equilibria suggest that the residual melts from which the amphiboles crystallized contained 3% 4% H2O, and adjustments for fractional crystallization suggest that the initial melts may have contained as much as 2% H2O. H2O contents of this magnitude would require substantial revision of the nearly anhydrous models for Precambrian high-MgO melts, possibly permitting generation at lower temperatures and pressures, lowering their densities and viscosities, increasing their eruptibility, and enhancing the formation of spinifex textures.

Field and Experimental Constraints on the Dynamics of Replenished Silicic Magma Chambers

NASA Astrophysics Data System (ADS)

Bain, A. A.; Jellinek, M.

2008-12-01

The underlying causes of catastrophic caldera-forming volcanic eruptions remain poorly understood. However, the occurrence of magma mixing within bimodal systems has become increasingly linked with such eruptions. In particular, buoyancy effects related to unstable density contrasts arising as a result of silicic- basaltic magma interactions may play an important role in the growth, differentiation and catastrophic eruption of silicic magma chambers. Evidence of such magmatic interactions can be found in layered intrusions from the Coastal Maine Magmatic Province (USA), where well-exposed cross-sections reveal hundreds of laterally-extensive basaltic sheets, apparently injected as intrusive lava flows onto the growing floors of silicic magma chambers. Interfaces between mafic and silicic layers are commonly sharply defined and exhibit deformation parallel to the inferred direction of palaeo-gravity. Our field observations suggest that the cooling, settling and buckling of gravitationally-unstable mafic replenishments may have driven large-scale (basalt layer depth) and small- scale (crystal diameter) upwelling and/or overturning of underlying buoyant silicic cumulate material. In order to characterize the full range of buoyancy effects, we carried out extensive spectral analysis of high- resolution digital field measurements from the Pleasant Bay and Mount Desert Island intrusions. In many cases, Rayleigh-Taylor theory and the longest measured wavelength of deformation indicate that a large and potentially-quantifiable fraction of the original, pre-replenishment silicic cumulate thickness may be missing, implying that vertical mass transfer has occurred. In addition, the shortest wavelengths of deformation are generally consistent with observed length-scales of crystals and clumps of crystals at these localities. With the aim of understanding the initial conditions that gave rise to these field observations, we conduct a series of laboratory experiments in which we observe the development of a Rayleigh-Taylor instability between a buoyant basal fluid layer overlain by a denser fluid layer. In order to identify the important parameters in the problem, we perform these experiments for a wide range of density contrasts, layer thicknesses and fluid rheologies (i.e. we vary particle concentration from the dilute to highly-crystalline limits to simulate freezing basalt and re-heated silicic cumulate rheologies). Regimes in which the entire silicic layer becomes unstable are potentially responsible for overturning the system and iniating large volcanic eruptions.

Transformations between Extensive and Intensive Versions of Thermodynamic Relationships

ERIC Educational Resources Information Center

Eberhart, James G.

2010-01-01

Most thermodynamic properties are either extensive (e.g., volume, energy, entropy, amount, etc.) or intensive (e.g., temperature, pressure, chemical potential, mole fraction, etc.). By the same token most of the mathematical relationships in thermodynamics can be written in extensive or intensive form. The basic laws of thermodynamics are usually…

Self-reporting inhibitors: single crystallization process to get two optically pure enantiomers.

PubMed

Wan, Xinhua; Ye, Xichong; Cui, Jiaxi; Li, Bowen; Li, Na; Zhang, Jie

2018-05-22

Collection of two optically pure enantiomers in a single crystallization process can significantly increase the chiral separation efficiency but it's hard to realize nowadays. Herein we describe, for the first time, a self-reporting strategy for visualizing the crystallization process by a kind of dyed self-assembled inhibitors made from the copolymers with tri(ethylene glycol)-grafting polymethylsiloxane as main chains and poly(N6-methacryloyl-L-lysine) as side chains. When applied with seeds together for the fractional crystallization of conglomerates, the inhibitors can label the formation of the secondary crystals and guide us to completely separate the crystallization process of two enantiomers with colorless crystals as the first product and red crystals as the secondary product. This method leads to high optical purity of D/L-Asn·H2O (99.9 ee% for D-crystals and 99.5 ee% for L-crystals) in a single crystallization process. Moreover, it requires low feeding amount of additives and shows excellent recyclability. We foresee its great potential in developing novel chiral separation methods that can be used in different scales. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Melting behavior and phase relations of lunar samples. [Apollo 12 rock samples

NASA Technical Reports Server (NTRS)

Hays, J. F.

1975-01-01

Cooling rate studies of 12002 were conducted and the results interpreted in terms of the crystallization history of this rock and certain other picritic Apollo 12 samples. Calculations of liquid densities and viscosities during crystallization, crystal settling velocities, and heat loss by the parent rock body are discussed, as are petrographic studies of other Apollo 12 samples. The process of magmatic differentiation that must have accompanied the early melting and chemical fractionation of the moon's outer layers was investigated. The source of regions of both high- and low-titanium mare basalts were also studied.

Crystal accumulation in the Hanford Waste Treatment Plant high level waste melter: Summary of 2017 experiments

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

Fox, K.; Fowley, M.

A full-scale, transparent mock-up of the Hanford Tank Waste Treatment and Immobilization Project High Level Waste glass melter riser and pour spout has been constructed to allow for testing with visual feedback of particle settling, accumulation, and resuspension when operating with a controlled fraction of crystals in the glass melt. Room temperature operation with silicone oil and magnetite particles simulating molten glass and spinel crystals, respectively, allows for direct observation of flow patterns and settling patterns. The fluid and particle mixture is recycled within the system for each test.

Extraordinary absorption of sound in porous lamella-crystals.

PubMed

Christensen, J; Romero-García, V; Picó, R; Cebrecos, A; de Abajo, F J García; Mortensen, N A; Willatzen, M; Sánchez-Morcillo, V J

2014-04-14

We present the design of a structured material supporting complete absorption of sound with a broadband response and functional for any direction of incident radiation. The structure which is fabricated out of porous lamellas is arranged into a low-density crystal and backed by a reflecting support. Experimental measurements show that strong all-angle sound absorption with almost zero reflectance takes place for a frequency range exceeding two octaves. We demonstrate that lowering the crystal filling fraction increases the wave interaction time and is responsible for the enhancement of intrinsic material dissipation, making the system more absorptive with less material.

Extraordinary absorption of sound in porous lamella-crystals

PubMed Central

Christensen, J.; Romero-García, V.; Picó, R.; Cebrecos, A.; de Abajo, F. J. García; Mortensen, N. A.; Willatzen, M.; Sánchez-Morcillo, V. J.

2014-01-01

We present the design of a structured material supporting complete absorption of sound with a broadband response and functional for any direction of incident radiation. The structure which is fabricated out of porous lamellas is arranged into a low-density crystal and backed by a reflecting support. Experimental measurements show that strong all-angle sound absorption with almost zero reflectance takes place for a frequency range exceeding two octaves. We demonstrate that lowering the crystal filling fraction increases the wave interaction time and is responsible for the enhancement of intrinsic material dissipation, making the system more absorptive with less material. PMID:24728322

Influence of Oxidation in Starting Material Sn on Electric Transport Properties of SnSe Single Crystals

NASA Astrophysics Data System (ADS)

Yamashita, Aichi; Ogiso, Osamu; Matsumoto, Ryo; Tanaka, Masashi; Hara, Hiroshi; Tanaka, Hiromi; Takeya, Hiroyuki; Lee, Chul-Ho; Takano, Yoshihiko

2018-06-01

We found that the electronic transport property of SnSe single crystals was sensitively affected by oxidation in raw Sn. Semiconducting SnSe single crystals were obtained by using Sn of grain form as a starting material while powder Sn resulted in metallic SnSe. X-ray photoelectron spectroscopy analysis revealed that the surfaces of raw Sn were oxidized, which volume fraction is lower in grain Sn. This indicates that the amount of oxygen in raw Sn is the key factor for the electronic transport property of SnSe.

Phase behavior of blends of linear and branched polyethylenes in the molten and solid states by small-angle neutron scattering

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

Alamo, R.G.; Mandelkern, L.; Londono, J.D.

1994-01-17

The state of mixing in blends of high-density polyethylene (HDPE) and low-density polyethylene (LDPE) in the liquid and solid state has been examined by small-angle neutron scattering (SANS) in conjunction with deuterium labeling. In the melt, SANS results indicate that HDPE/LDPE mixtures from a single-phase solution for all concentrations, including blends containing high volume fractions ([phi] > 0.5) of branched polymer, for which multiphase melts have previously been suggested. Proper accounting for isotope effects is essential to avoid artifacts, because the H/D interaction parameter is sufficiently large ([sub [chi]HD] [approximately] 4 [times] 10[sup [minus]4]) to cause phase separation in themore » amorphous state for molecular weights (MW) >150,000. In the solid state, after slow cooling from the melt ([approximately]0.75 C/min), the HDPE/LDPE system shows extensive segregation into separate domains [approximately]100--300 [angstrom] in size. Both the shape and magnitude of the absolute scattering cross section are consistent with the conclusion that the components are extensively segregated into separate lamellae. Two-peak melting curves obtained for such mixtures support the SANS interpretation, and the segregation of components in the solid state is therefore a consequence of crystallization mechanisms rather than incompatibility in the liquid state.« less

Length-scale dependent transport properties of colloidal and protein solutions for prediction of crystal nucleation rates

NASA Astrophysics Data System (ADS)

Kalwarczyk, Tomasz; Sozanski, Krzysztof; Jakiela, Slawomir; Wisniewska, Agnieszka; Kalwarczyk, Ewelina; Kryszczuk, Katarzyna; Hou, Sen; Holyst, Robert

2014-08-01

We propose a scaling equation describing transport properties (diffusion and viscosity) in the solutions of colloidal particles. We apply the equation to 23 different systems including colloids and proteins differing in size (range of diameters: 4 nm to 1 μm), and volume fractions (10-3-0.56). In solutions under study colloids/proteins interact via steric, hydrodynamic, van der Waals and/or electrostatic interactions. We implement contribution of those interactions into the scaling law. Finally we use our scaling law together with the literature values of the barrier for nucleation to predict crystal nucleation rates of hard-sphere like colloids. The resulting crystal nucleation rates agree with existing experimental data.We propose a scaling equation describing transport properties (diffusion and viscosity) in the solutions of colloidal particles. We apply the equation to 23 different systems including colloids and proteins differing in size (range of diameters: 4 nm to 1 μm), and volume fractions (10-3-0.56). In solutions under study colloids/proteins interact via steric, hydrodynamic, van der Waals and/or electrostatic interactions. We implement contribution of those interactions into the scaling law. Finally we use our scaling law together with the literature values of the barrier for nucleation to predict crystal nucleation rates of hard-sphere like colloids. The resulting crystal nucleation rates agree with existing experimental data. Electronic supplementary information (ESI) available: Experimental and some analysis details. See DOI: 10.1039/c4nr00647j

Developing a Theoretical Framework for Examining Student Understanding of Fractional Concepts: An Historical Accounting

ERIC Educational Resources Information Center

Cooper, Susan M.; Wilkerson, Trena L.; Montgomery, Mark; Mechell, Sara; Arterbury, Kristin; Moore, Sherrie

2012-01-01

In 2007, a group of mathematics educators and researchers met to examine rational numbers and why children have such an issue with them. An extensive review of the literature on fractional understanding was conducted. The ideas in that literature were then consolidated into a theoretical framework for examining fractions. Once that theoretical…

Crystal Growth of ZnSe and Related Ternary Compound Semiconductors by Vapor Transport

NASA Technical Reports Server (NTRS)

Su, Ching-Hua; Brebrick, R. F.; Burger, A.; Dudley, M.; Ramachandran, N.

2003-01-01

The objective of the project is to determine the relative contributions of gravity-driven fluid flows to the compositional distribution, incorporation of impurities and defects, and deviation from stoichiometry observed in the crystals grown by vapor transport as results of buoyance-driven convection and growth interface fluctuations caused by irregular fluid-flows. ZnSe and related ternary compounds, such as ZnSeS and ZnSeTe, were grown by vapor transport technique with real time in-situ non-invasive monitoring techniques. The grown crystals were characterized extensively to correlate the grown crystal properties with the growth conditions.

Lithium in Jack Hills zircons: Evidence for extensive weathering of Earth's earliest crust

NASA Astrophysics Data System (ADS)

Ushikubo, Takayuki; Kita, Noriko T.; Cavosie, Aaron J.; Wilde, Simon A.; Rudnick, Roberta L.; Valley, John W.

2008-08-01

In situ Li analyses of 4348 to 3362 Ma detrital zircons from the Jack Hills, Western Australia by SIMS reveal that the Li abundances (typically 10 to 60 ppm) are commonly over 10,000 times higher than in zircons crystallized from mantle-derived magmas and in mantle-derived zircon megacrysts (typically < 2 ppb). High Li concentrations in zircons (10 to 250 ppm) have also been found in igneous zircons from three continental parent rocks: granites, Li-rich pegmatites, and migmatites in pelitic metasediment. The substitution of trivalent cations (REEs and Y) in zircon correlates with Li + 1 and P + 5 , suggesting that an interstitial site for Li, as well as the xenotime substitution for P, provides charge balance for REEs. Li is thus fixed in the zircon structure by coupled substitutions, and diffusive changes in [Li] composition are rate-limited by slow diffusion of REEs. The Jack Hills zircons also have fractionated lithium isotope ratios ( δ7Li = - 19 to + 13‰) about five times more variable than those recorded in primitive ocean floor basalts (2 to 8‰), but similar to continental crust and its weathering products. Values of δ7Li below - 10‰ are found in zircons that formed as early as 4300 Ma. The high Li compositions indicate that primitive magmas were not the source of Jack Hills zircons and the fractionated values of δ7Li suggest that highly weathered regolith was sampled by these early Archean magmas. These new Li data provide evidence that the parent magmas of ancient zircons from Jack Hills incorporated materials from the surface of the Earth that interacted at low temperature with liquid water. These data support the hypothesis that continental-type crust and oceans existed by 4300 Ma, within 250 million years of the formation of Earth and the low values of δ7Li suggest that weathering was extensive in the early Archean.

Nature of the magma storage system beneath the Damavand volcano (N. Iran): An integrated study

NASA Astrophysics Data System (ADS)

Eskandari, Amir; Amini, Sadraddin; De Rosa, Rosanna; Donato, Paola

2018-02-01

Damavand intraplate stratovolcano constructed upon a moderately thick crust (58-67 km) over the last 2 Ma. The erupted products are dominantly trachyandesite-trachyte (TT) lavas and pyroclasts, with minor mafic magmas including tephrite-basanite-trachybasalt and alkali olivine basalts emplaced as cinder cones at the base of the stratovolcano. The TT products are characterized by a mineral assemblage of clinopyroxene (diopside-augite), orthopyroxene (clinoenstatite), feldspar (An2-58, Ab6-69, Or2-56), high Ti phlogopite, F-apatite, Fesbnd Ti oxides, and minor amounts of olivine (Fo73-80), amphibole and zircon, whereas olivine (Fo78-88), high Mg# (80-89) diopside, feldspar, apatite and Fesbnd Ti oxide occur in the mafic magmas. The presence of hydrous and anhydrous minerals, normal zonings, mafic cumulates, and the composition of magmatic inclusions in the TT products suggest evolutionary processes in polybaric conditions. In the same way, disequilibrium textures - including orthopyroxene mantled with clinopyroxene, reaction rim of phlogopite and amphibole, the coexistence of olivine and orthopyroxene, reverse, oscillatory and complex zonings of pyroxene and feldspar crystals - suggest magmatic evolutions in open systems with a varying temperature, oxygen fugacity, water as well as pressure and, to a lesser extent, melt chemistry. Mineral assemblages are used to model the physicochemical conditions and assess default parameters for the thermodynamic simulation of crystallization using MELTS software to track the P-T-H2O-ƒO2 evolution of the magma plumbing system. Thermobarometry and MELTS models estimated the initial nucleation depth at 16-17 kb (56-60 km) for olivine (Fo89) and high Al diopside crystals occurring in the mafic primary magma; it then stopped and underwent fractionation between 8 and 10 kb (28-35 km), corresponding with Moho depth, and continued to differentiate in the lower crust, in agreement with the geophysical models. The mafic rocks were formed by crystal fractionation from the reconstructed primary magma (13 wt% MgO) with the minor role of recharge and crustal assimilation. Phenocrysts in TT lavas recorded a wide range of temperature and pressure of crystallization; at least three main levels of magma storage can be recognized according to the statistical analysis of the models, at 6-8 kb (22-28 km), 4-6 kb (15-22 km), and 0.6-3 kb (2-11 km), respectively. The temperature of crystallization ranged from 1430 to 1180 °C for primary mafic magma to alkali olivine basalts and 1180-800 °C for TT suite. According to the current geophysical models, the present structure of the magma storage system in the crust beneath the Damavand volcano consists of three major accumulation zones located at 20 km, 6-8 km and 3-4.5 km depth. Our data enlarge this scenario, suggesting a more complex magma storage system strongly controlled by the transpressional tectonic regime. Multi-depth magma reservoirs may account for the local thickening of crust below the volcano. The polybaric fractionation model, using the MELTS algorithm, reproduces mineralogy and chemical variations of minerals and whole rock of the Damavand TT lavas. However, some discrepancies between major elements of models and trends of data can be ascribed to the recharge of more mafic magma, minor crustal assimilation, disaggregation of crystal-rich mushes and uptake of magmatic inclusions, as well as crystals from different crustal levels. The polybaric differentiation as the fractionation and/or accumulation of crystals was the probable mechanism for explaining the scarcity of mafic volcanic rocks at the Damavand volcano.

Crystallization in lactose refining-a review.

PubMed

Wong, Shin Yee; Hartel, Richard W

2014-03-01

In the dairy industry, crystallization is an important separation process used in the refining of lactose from whey solutions. In the refining operation, lactose crystals are separated from the whey solution through nucleation, growth, and/or aggregation. The rate of crystallization is determined by the combined effect of crystallizer design, processing parameters, and impurities on the kinetics of the process. This review summarizes studies on lactose crystallization, including the mechanism, theory of crystallization, and the impact of various factors affecting the crystallization kinetics. In addition, an overview of the industrial crystallization operation highlights the problems faced by the lactose manufacturer. The approaches that are beneficial to the lactose manufacturer for process optimization or improvement are summarized in this review. Over the years, much knowledge has been acquired through extensive research. However, the industrial crystallization process is still far from optimized. Therefore, future effort should focus on transferring the new knowledge and technology to the dairy industry. © 2014 Institute of Food Technologists®

Inclined monochromator for high heat-load synchrotron x-ray radiation

DOEpatents

Khounsary, A.M.

1994-02-15

A double crystal monochromator is described including two identical, parallel crystals, each of which is cut such that the normal to the diffraction planes of interest makes an angle less than 90 degrees with the surface normal. Diffraction is symmetric, regardless of whether the crystals are symmetrically or asymmetrically cut, enabling operation of the monochromator with a fixed plane of diffraction. As a result of the inclination of the crystal surface, an incident beam has a footprint area which is elongated both vertically and horizontally when compared to that of the conventional monochromator, reducing the heat flux of the incident beam and enabling more efficient surface cooling. Because after inclination of the crystal only a fraction of thermal distortion lies in the diffraction plane, slope errors and the resultant misorientation of the diffracted beam are reduced. 11 figures.

High alumina (HA) and very high potassium (VHK) basalt clasts from Apollo 14 breccias. I - Mineralogy and Petrology - Evidence of crystallization from evolving magmas

NASA Technical Reports Server (NTRS)

Neal, C. R.; Taylor, L. A.; Patchen, A. D.

1989-01-01

The mineralogy and petrography of very high potassium (VHK) and high alumina (HA) basalts from the Apollo 14 site provide an insight into their magmatic evolution. Generally, their parageneses are similar, with olivine and chromite the early liquidus phases, followed by plagioclase and pyroxene, which crystallized together. Although late-stage ilmenite and FeNi metal occur in both VHK and HA samples, the VHKs also crystallize K-feldspar and Fa-rich olivine. Zoning of constituent minerals is similar for both basalt types, demonstrating that the parental magmas for both HA and VHK basalts became enriched in K, Na, Ca, Fe, and Ti and depleted in Mg and Al as crystallization proceeded. Enrichment of K in the VHK basalts is above that expected from normal fractional crystallization.

Inclined monochromator for high heat-load synchrotron x-ray radiation

DOEpatents

Khounsary, Ali M.

1994-01-01

A double crystal monochromator including two identical, parallel crystals, each of which is cut such that the normal to the diffraction planes of interest makes an angle less than 90 degrees with the surface normal. Diffraction is symmetric, regardless of whether the crystals are symmetrically or asymmetrically cut, enabling operation of the monochromator with a fixed plane of diffraction. As a result of the inclination of the crystal surface, an incident beam has a footprint area which is elongated both vertically and horizontally when compared to that of the conventional monochromator, reducing the heat flux of the incident beam and enabling more efficient surface cooling. Because after inclination of the crystal only a fraction of thermal distortion lies in the diffraction plane, slope errors and the resultant misorientation of the diffracted beam are reduced.

Continued fractions with limit periodic coefficients

NASA Astrophysics Data System (ADS)

Buslaev, V. I.

2018-02-01

The boundary properties of functions represented by limit periodic continued fractions of a fairly general form are investigated. Such functions are shown to have no single-valued meromorphic extension to any neighbourhood of any non-isolated boundary point of the set of convergence of the continued fraction. The boundary of the set of meromorphy has the property of symmetry in an external field determined by the parameters of the continued fraction. Bibliography: 26 titles.

Photoluminescence spectral reliance on aggregation order of 1,1-Bis(2'-thienyl)-2,3,4,5-tetraphenylsilole.

PubMed

Chen, Junwu; Xu, Bin; Yang, Kaixia; Cao, Yong; Sung, Herman H Y; Williams, Ian D; Tang, Ben Zhong

2005-09-15

1,1-Bis(2'-thienyl)-2,3,4,5-tetraphenylsilole (1) was prepared and characterized crystallographically. Silole 1 exhibited aggregation-induced emission (AIE) behavior like other 2,3,4,5-tetraphenylsiloles. Unexpectedly, aggregates formed in water/acetone (6:4 by volume) mixture emitted a blue light that peaked at 474 nm, while aggregates formed in the mixtures with higher water fractions emitted green light that peaked at 500 nm. Transmission electron microscopy demonstrated that the aggregates formed in the mixture with water fraction of 60% were single crystals, while aggregates that formed in the mixture with water fraction of 90% were irregular and poorly ordered particles. The unusual PL spectral reliance on aggregation order was further confirmed by PL emissions of macroscopic crystal powders and amorphous powders of the silole in the dry state. PL spectral blue shifting was observed upon aging of the poorly ordered aggregates formed in mixtures with water fractions of 70-90%, and they finally exhibited the same blue emission as the crystalline aggregates. The as-deposited thin solid film was amorphous and it could be transformed to a transparent crystalline film upon treatment in the vapor of an ethanol/water (1:1 by volume) mixture, along with PL spectral blue shifting due to changing of aggregation order. It was also found that the crystalline film showed a blue-shifted absorption spectrum relative to the amorphous film and the shift of the absorption edge of the spectra could match that of corresponding PL spectra. The FT-IR spectrum of crystal powders of 1 displayed more vibration modes compared with that of amorphous powders, suggesting the existence of different pi-overlaps or different molecular conformations. The crystals of 1-methyl-1,2,3,4,5-pentaphenylsilole and hexaphenylsilole also showed blue-shifted PL emissions of their amorphous solids, with a comparable PL spectral shift of 1. Developing of a silole solution on a TLC plate readily brought about an amorphous thin layer. Our results suggest that crystalline films of AIE-active siloles are potential emissive layers for efficient blue OLEDs with stable color and long lifetime.

Purification, crystallization and preliminary X-ray analysis of urease from pigeon pea (Cajanus cajan).

PubMed

Balasubramanian, Anuradha; Ponnuraj, Karthe

2008-07-01

Urease is a seed protein that is common to most Leguminosae. It also occurs in many bacteria, fungi and several species of yeast. Urease catalyzes the hydrolysis of urea to ammonia and carbon dioxide, thus allowing organisms to use exogenous and internally generated urea as a nitrogen source. Urease from pigeon pea seeds has been purified to electrophoretic homogeneity using a series of steps involving ammonium sulfate fractionation, acid precipitation, ion-exchange and size-exclusion chromatography techniques. The pigeon pea urease was crystallized and the resulting crystals diffracted to 2.5 A resolution. The crystals belong to the rhombohedral space group R32, with unit-cell parameters a = b = 176.29, c = 346.44 A.

Crystallization of Polymers Investigated by Temperature-Modulated DSC

PubMed Central

Righetti, Maria Cristina

2017-01-01

The aim of this review is to summarize studies conducted by temperature-modulated differential scanning calorimetry (TMDSC) on polymer crystallization. This technique can provide several advantages for the analysis of polymers with respect to conventional differential scanning calorimetry. Crystallizations conducted by TMDSC in different experimental conditions are analysed and discussed, in order to illustrate the type of information that can be deduced. Isothermal and non-isothermal crystallizations upon heating and cooling are examined separately, together with the relevant mathematical treatments that allow the evolution of the crystalline, mobile amorphous and rigid amorphous fractions to be determined. The phenomena of ‘reversing’ and ‘reversible‘ melting are explicated through the analysis of the thermal response of various semi-crystalline polymers to temperature modulation. PMID:28772807

Crystallization and Melt Removal at Arenal Volcano, Polytopic Vector Analysis

NASA Astrophysics Data System (ADS)

Hidalgo, P. J.; Vogel, T. A.; Bolge, L. L.; Ehrlich, R.; Alvarado, G. E.

2007-12-01

Tephra sequences ET3 and ET4 from Arenal volcano in Costa Rica have recently been interpreted to be a product of crystal fractionation by Bolge and coworkers in a series of papers (2004, 2006). The two tephra units are part of a sequence of 22 tephra units that represent a 7000 year span of the Arenal volcano activity. The tephro- stratigraphy has been described extensively by Melson (1982; 1994). The ET3 and ET4 tephras were interpreted (based on major- and trace-element, isotopic analyses of whole rocks and microchemical analyses of individual phases) as clear evidence of crystal separation by gravity settling (Bolge et al., 2004, 2006). The lower ET4 tephra sequence (andesitic and crystal poor) and the upper ET3 tephra (basaltic and crystal rich) represent an inverted snapshot of the magma chamber with contrasting geochemical properties. The ET3 sequence (deeper part of the magma chamber) has nearly constant composition with only a few elements varying stratigraphically (best represented by CaO). This is consistent with gradually decreasing amounts of melt in the upper part of ET3. The lower ET4 tephra (upper part of the magma chamber) contains large chemical gradients in both incompatible and compatible elements. In the present study we use whole-rock geochemical data from the recent tephra sequences ET3 and ET4 as inputs to Polytopic Vector Analysis (PVA) (for a review of this method see Vogel and coworkers, in press). With this method we produce a three end member solution that is consistent with crystallization of Olivine, plagioclase and pyroxene from the most mafic end member (EM1) resulting in a crystal rich mush zone. As crystallization progresses the compositions of the liquids are driven towards an intermediate end member (EM3), which has an intermediate composition liquid. At EM3 composition, rapid depletion of FeO, MgO and TiO2 by crystallization of Fe-Ti oxides, rapidly drives the liquid composition towards the silicic EM1 (incompatible element enriched end member). Using PVA we refine the interpretations of Bolge and coworkers and show that melt from the crystalline rich ET3 tephra was removed and ponded in the magma chamber above the crystalline mush (top part of ET4 unit). Thus when the eruption occurred the most evolved tephra (ET4) were deposited first followed by the least evolved tephra (ET3), which resulted in sampling of a chemically zoned magma chamber. Using PVA on stratigraphically controlled whole-rock analyses of tephra samples, we can unambiguously identify processes and end members that are involved in crystal accumulation and liquid separation processes. Thus PVA is a rigorous analytical tool that uses only whole-rock chemical data to produce robust results that can be used with other analytical techniques to test petrological models.

Intracrystalline site preference of hydrogen isotopes in borax

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

Pradhananga, T.M.; Matsuo, S.

1985-01-03

The total hydrogen involved in borax synthesized at 25/sup 0/C in aqueous solution is enriched in deuterium by 5.3% compared with the mother liquor. There is no change in the value of the D/H fractionation factor between the hydrogen in borax and those in the mother liquor with changes in the degree of supersaturation. The fractionation factor changes slightly with a change in the crystallization temperature of borax in the range from 5 to 25/sup 0/C. The D/H ratio in the different sites of borax was estimated by a fractional dehydration technique. The results show that hydrogen atoms of themore » polyanionic group (B/sub 4/O/sub 5/(OH)/sub 4/) are much more enriched in deuterium than those of the cationic group (Na/sub 2/ x 8H/sub 2/O). The delta D values, referred to the mother liquor from which the borax was crystallized, for the cationic group (site A) and the polyanionic group (site B) are -35 +/- 3 and 167 +/- 13%, respectively based on the fractional dehydration results obtained at -21/sup 0/C. At -21/sup 0/C, isotopic exchange between different sites during dehydration is assumed not to occur. The mechanism for dehydration of borax is discussed. 48 references, 8 figures, 3 tables.« less

Lithosphere destabilization by melt percolation during pre-oceanic rifting: Evidence from Alpine-Apennine ophiolitic peridotites

NASA Astrophysics Data System (ADS)

Piccardo, Giovanni; Ranalli, Giorgio

2017-04-01

Orogenic peridotites from Alpine-Apennine ophiolite Massifs (Lanzo, Voltri, External and Internal Ligurides, - NW Italy, and Mt. Maggiore - Corsica) derive from the mantle lithosphere of the Ligurian Tethys. Field/structural and petrologic/geochemical studies provide constraints on the evolution of the lithospheric mantle during pre-oceanic passive rifting of the late Jurassic Ligurian Tethys ocean. Continental rifting by far-field tectonic forces induced extension of the lithosphere by means of km-scale extensional shear zones that developed before infiltration of melts from the asthenosphere (Piccardo and Vissers, 2007). After significant thinning of the lithosphere, the passively upwelling asthenosphere underwent spinel-facies decompression melting along the axial zone of the extensional system. Silica-undersaturated melt fractions percolated through the lithospheric mantle via diffuse/focused porous flow and interacted with the host peridotite through pyroxenes-dissolving/olivine-precipitating melt/rock reactions. Pyroxene dissolution and olivine precipitation modified the composition of the primary silica-undersaturated melts into derivative silica-saturated melts, while the host lithospheric spinel lherzolites were transformed into pyroxene-depleted/olivine-enriched reactive spinel harzburgites and dunites. The derivative liquids interacted through olivine-dissolving/orthopyroxene+plagioclase-crystallizing reactions with the host peridotites that were impregnated and refertilized (Piccardo et al., 2015). The saturated melts stagnated and crystallized in the shallow mantle lithosphere (as testified by diffuse interstitial crystallization of euhedral orthopyroxene and anhedral plagioclase) and locally ponded, forming orthopyroxene-rich/olivine-free gabbro-norite pods (Piccardo and Guarnieri, 2011). Reactive and impregnated peridotites are characterized by high equilibration temperatures (up to 1250 °C) even at low pressure, plagioclase-peridotite facies conditions. This indicates that thermal advection by percolation of hot asthenospheric melts significantly heated the lithospheric mantle column above the melting asthenosphere. Numerical and analogue models show that infiltration of melts results in considerable softening of mantle rocks. Total ithospheric strength can be decreased from 10 to 1 TN m-1 as orders of magnitude and the sin-rift thermo-mechanical erosion of the lithospheric mantle induces significant rheological softening along the axial zone of extension (Corti et al., 2007; Ranalli et al., 2007). Softening of the lithospheric mantle may lead to whole lithospheric failure and consequently to transition from continental extension to oceanic spreading. Therefore, rheological softening caused destabilization of the lithospheric mantle between the future continental margins (Piccardo et al., 2014; Piccardo, 2016) of the Ligurian Tethys. The wedge of destabilized lithosphere favored faster divergence of the continental blocks and enhanced doming and thermal buoyancy of deeper/hotter asthenosphere that rose between the future continental margins and originated aggregated MORB melts (i.e., the oceanic magmatism that formed olivine-gabbro intrusions and pillowed basalt extrusions). Lithosphere destabilization by melt percolation can play a fundamental role in the geodynamic evolution of lithosphere extension causing transition from continental extension to continental break-up to oceanic spreading. Corti, G., Bonini, M., Innocenti, F., Manetti, P., Piccardo, G.B., Ranalli, G., 2007. Journal of Geodynamics, 43, 465-483. Piccardo, G.B., Padovano, M., Guarnieri, L. 2014. Earth-Science Reviews, 138, 409-434. Piccardo, G.B., 2016. Gondwana Research, 39, 230-249. Piccardo, G.B., Vissers, R.L.M., 2007. Journal of Geodynamics, 43, 417-449. Piccardo, G.B., Guarnieri, L., 2011. Lithos, 124, 210-214. Ranalli, G., Piccardo, G.B., Corona-Chavez, P., 2007. Journal of Geodynamics, 43, 450-464.

AIP1OGREN: Aerosol Observing Station Intensive Properties Value-Added Product

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

Koontz, Annette; Flynn, Connor

The aip1ogren value-added product (VAP) computes several aerosol intensive properties. It requires as input calibrated, corrected, aerosol extensive properties (scattering and absorption coefficients, primarily) from the Aerosol Observing Station (AOS). Aerosol extensive properties depend on both the nature of the aerosol and the amount of the aerosol. We compute several properties as relationships between the various extensive properties. These intensive properties are independent of aerosol amount and instead relate to intrinsic properties of the aerosol itself. Along with the original extensive properties we report aerosol single-scattering albedo, hemispheric backscatter fraction, asymmetry parameter, and Ångström exponent for scattering and absorption withmore » one-minute averaging. An hourly averaged file is produced from the 1-minute files that includes all extensive and intensive properties as well as submicron scattering and submicron absorption fractions. Finally, in both the minutely and hourly files the aerosol radiative forcing efficiency is provided.« less

Research progress on laser crystals in China

NASA Astrophysics Data System (ADS)

Yingxia, Z.

1985-01-01

Current Chinese research on laser crystals is now quite extensive and involves more than 30 research teams with nearly 1,000 technicians and workers actively engaged in the study of more than 20 types of laser cyrstals. Neodymium-doped yttrium aluminum garnet (Nd:YAG) and ruby (Cr:Al2O3) lasers have been manufactured and are widely employed. There are several new and promising crystals now under study which will find applications, and both basic and exploratory research have given rise to new developments.

Light propagation in two-dimensional photonic crystals based on uniaxial polar materials: results on polaritonic spectrum

NASA Astrophysics Data System (ADS)

Gómez-Urrea, H. A.; Duque, C. A.; Pérez-Quintana, I. V.; Mora-Ramos, M. E.

2017-03-01

The dispersion relations of two-dimensional photonic crystals made of uniaxial polaritonic cylinders arranged in triangular lattice are calculated. The particular case of the transverse magnetic polarization is taken into account. Three different uniaxial materials showing transverse phonon-polariton excitations are considered: aluminum nitride, gallium nitride, and indium nitride. The study is carried out by means of the finite-difference time-domain technique for the solution of Maxwell equations, together with the method of the auxiliary differential equation. It is shown that changing the filling fraction can result in the modification of both the photonic and polaritonic bandgaps in the optical dispersion relations. Wider gaps appear for smaller filling fraction values, whereas a larger number of photonic bandgaps will occur within the frequency range considered when a larger filling fraction is used. The effect of including the distinct wurtzite III-V nitride semiconductors as core materials in the cylinders embedded in the air on the photonic properties is discussed as well, highlighting the effect of the dielectric anisotropy on the properties of the polaritonic part of the photonic spectrum.

Current transport mechanism in graphene/AlGaN/GaN heterostructures with various Al mole fractions

NASA Astrophysics Data System (ADS)

Pandit, Bhishma; Seo, Tae Hoon; Ryu, Beo Deul; Cho, Jaehee

2016-06-01

The current transport mechanism of graphene formed on AlxGa1-xN/GaN heterostructures with various Al mole fractions (x = 0.15, 0.20, 0.30, and 0.40) is investigated. The current-voltage measurement from graphene to AlGaN/GaN shows an excellent rectifying property. The extracted Schottky barrier height of the graphene/AlGaN/GaN contacts increases with the Al mole fraction in AlGaN. However, the current transport mechanism deviates from the Schottky-Mott theory owing to the deterioration of AlGaN crystal quality at high Al mole fractions confirmed by reverse leakage current measurement.

Out-of-equilibrium processes in suspensions of oppositely charged colloids: liquid-to-crystal nucleation and gel formation

NASA Astrophysics Data System (ADS)

Sanz, Eduardo

2009-03-01

We study the kinetics of the liquid-to-crystal transformation and of gel formation in colloidal suspensions of oppositely charged particles. We analyse, by means of both computer simulations and experiments, the evolution of a fluid quenched to a state point of the phase diagram where the most stable state is either a homogeneous crystalline solid or a solid phase in contact with a dilute gas. On the one hand, at high temperatures and high packing fractions, close to an ordered-solid/disordered-solid coexistence line, we find that the fluid-to-crystal pathway does not follow the minimum free energy route. On the other hand, a quench to a state point far from the ordered-crystal/disordered-crystal coexistence border is followed by a fluid-to-solid transition through the minimum free energy pathway. At low temperatures and packing fractions we observe that the system undergoes a gas-liquid spinodal decomposition that, at some point, arrests giving rise to a gel-like structure. Both our simulations and experiments suggest that increasing the interaction range favors crystallization over vitrification in gel-like structures. [4pt] In collaboration with Chantal Valeriani, Soft Condensed Matter, Debye Institute for Nanomaterials Science, Utrecht University, Princetonplein 5, 3584 CC Utrecht, The Netherlands and SUPA, School of Physics, University of Edinburgh, JCMB King's Buildings, Mayfield Road, Edinburgh EH9 3JZ, UK; Teun Vissers, Andrea Fortini, Mirjam E. Leunissen, and Alfons van Blaaderen, Soft Condensed Matter, Debye Institute for Nanomaterials Science, Utrecht University; Daan Frenke, FOM Institute for Atomic and Molecular Physics, Kruislaan 407, 1098 SJ Amsterdam, The Netherlands and Department of Chemistry, University of Cambridge, Lensfield Road, CB2 1EW, Cambridge, UK; and Marjolein Dijkstra, Soft Condensed Matter, Debye Institute for Nanomaterials Science, Utrecht University.

Calcite growth-rate inhibition by fulvic acids isolated from Big Soda Lake, Nevada, USA, The Suwannee River, Georgia, USA and by polycarboxylic acids

USGS Publications Warehouse

Reddy, Michael M.; Leenheer, Jerry

2011-01-01

Calcite crystallization rates are characterized using a constant solution composition at 25°C, pH=8.5, and calcite supersaturation (Ω) of 4.5 in the absence and presence of fulvic acids isolated from Big Soda Lake, Nevada (BSLFA), and a fulvic acid from the Suwannee River, Georgia (SRFA). Rates are also measured in the presence and absence of low-molar mass, aliphatic-alicyclic polycarboxylic acids (PCA). BSLFA inhibits calcite crystal-growth rates with increasing BSLFA concentration, suggesting that BSLFA adsorbs at growth sites on the calcite crystal surface. Calcite growth morphology in the presence of BSLFA differed from growth in its absence, supporting an adsorption mechanism of calcite-growth inhibition by BSLFA. Calcite growth-rate inhibition by BSLFA is consistent with a model indicating that polycarboxylic acid molecules present in BSLFA adsorb at growth sites on the calcite crystal surface. In contrast to published results for an unfractionated SRFA, there is dramatic calcite growth inhibition (at a concentration of 1 mg/L) by a SRFA fraction eluted by pH 5 solution from XAD-8 resin, indicating that calcite growth-rate inhibition is related to specific SRFA component fractions. A cyclic PCA, 1, 2, 3, 4, 5, 6-cyclohexane hexacarboxylic acid (CHXHCA) is a strong calcite growth-rate inhibitor at concentrations less than 0.1 mg/L. Two other cyclic PCAs, 1, 1 cyclopentanedicarboxylic acid (CPDCA) and 1, 1 cyclobutanedicarboxylic acid (CBDCA) with the carboxylic acid groups attached to the same ring carbon atom, have no effect on calcite growth rates up to concentrations of 10 mg/L. Organic matter ad-sorbed from the air onto the seed crystals has no effect on the measured calcite crystal-growth rates.

Orientation Dependence of Functional Properties in Heterophase Single Crystals of the Ti36.5Ni51.0Hf12.5 and Ti48.5Ni51.5 Alloys

NASA Astrophysics Data System (ADS)

Panchenko, E. Yu.; Chumlyakov, Yu. I.; Surikov, N. Yu.; Tagiltsev, A. I.; Vetoshkina, N. G.; Osipovich, K. S.; Maier, H.; Sehitoglu, H.

2016-03-01

The features of orientation dependence of stress-induced thermoelastic B2-( R)- B19'-martensitic transformations in single crystals of the Ti48.5Ni51.5 and Ni51.0Ti36.5Hf12.5 (at.%) alloys, which contain disperse particles of the Ti3Ni4 and H-phase, respectively, are revealed along with those of their shape-memory effects (SME) and superelasticity (SE). It is experimentally demonstrated that irrespective of the crystal structure of disperse particles measuring more than 100 nm, for their volume fraction f > 16% there is a weaker orientation dependence of the reversible strain in the cases of manifestation of SME and SE. In the orientations of Class I, wherein martensitic detwinning introduces a considerable contribution into transformation strain, the values of SME |ɛ SME | and SE |ɛ SE | decrease by over a factor of two compared to the theoretical lattice strain value |ɛ tr0 | for a B2- B19'-transformation and the experimental values of reversible strain for quenched TiNi crystals. In the orientations of Class 2, wherein detwinning of the martensite is suppressed as is the case in quenched single-phase single crystals, the reversible strain is maintained close to its theoretical value |ɛ tr0 |. Micromechanical models of interaction between the martensite and the disperse particles are proposed, which account for the weaker orientation dependence of |ɛ SME | and |ɛ SE | due to suppression of detwinning of the B19'-martensite crystals by the particles and a transition from a single-variant evolution of the stress-induced martensitic transformations to a multiple-variant evolution of transformations in the cases of increased size of the particles and their larger volume fractions.

Positron source position sensing detector and electronics

DOEpatents

Burnham, Charles A.; Bradshaw, Jr., John F.; Kaufman, David E.; Chesler, David A.; Brownell, Gordon L.

1985-01-01

A positron source, position sensing device, particularly with medical applications, in which positron induced gamma radiation is detected using a ring of stacked, individual scintillation crystals, a plurality of photodetectors, separated from the scintillation crystals by a light guide, and high resolution position interpolation electronics. Preferably the scintillation crystals are several times more numerous than the photodetectors with each crystal being responsible for a single scintillation event from a received gamma ray. The light guide will disperse the light emitted from gamma ray absorption over several photodetectors. Processing electronics for the output of the photodetectors resolves the location of the scintillation event to a fraction of the dimension of each photodetector. Because each positron absorption results in two 180.degree. oppositely traveling gamma rays, the detection of scintillation in pairs permits location of the positron source in a manner useful for diagnostic purposes. The processing electronics simultaneously responds to the outputs of the photodetectors to locate the scintillations to the source crystal. While it is preferable that the scintillation crystal include a plurality of stacked crystal elements, the resolving power of the processing electronics is also applicable to continuous crystal scintillators.

Space-Time Crystal and Space-Time Group

NASA Astrophysics Data System (ADS)

Xu, Shenglong; Wu, Congjun

2018-03-01

Crystal structures and the Bloch theorem play a fundamental role in condensed matter physics. We extend the static crystal to the dynamic "space-time" crystal characterized by the general intertwined space-time periodicities in D +1 dimensions, which include both the static crystal and the Floquet crystal as special cases. A new group structure dubbed a "space-time" group is constructed to describe the discrete symmetries of a space-time crystal. Compared to space and magnetic groups, the space-time group is augmented by "time-screw" rotations and "time-glide" reflections involving fractional translations along the time direction. A complete classification of the 13 space-time groups in one-plus-one dimensions (1 +1 D ) is performed. The Kramers-type degeneracy can arise from the glide time-reversal symmetry without the half-integer spinor structure, which constrains the winding number patterns of spectral dispersions. In 2 +1 D , nonsymmorphic space-time symmetries enforce spectral degeneracies, leading to protected Floquet semimetal states. We provide a general framework for further studying topological properties of the (D +1 )-dimensional space-time crystal.

Space-Time Crystal and Space-Time Group.

PubMed

Xu, Shenglong; Wu, Congjun

2018-03-02

Crystal structures and the Bloch theorem play a fundamental role in condensed matter physics. We extend the static crystal to the dynamic "space-time" crystal characterized by the general intertwined space-time periodicities in D+1 dimensions, which include both the static crystal and the Floquet crystal as special cases. A new group structure dubbed a "space-time" group is constructed to describe the discrete symmetries of a space-time crystal. Compared to space and magnetic groups, the space-time group is augmented by "time-screw" rotations and "time-glide" reflections involving fractional translations along the time direction. A complete classification of the 13 space-time groups in one-plus-one dimensions (1+1D) is performed. The Kramers-type degeneracy can arise from the glide time-reversal symmetry without the half-integer spinor structure, which constrains the winding number patterns of spectral dispersions. In 2+1D, nonsymmorphic space-time symmetries enforce spectral degeneracies, leading to protected Floquet semimetal states. We provide a general framework for further studying topological properties of the (D+1)-dimensional space-time crystal.

Crystallization of Hard Sphere Colloids in Microgravity: Results of the Colloidal Disorder-Order Transition, CDOT on USML-2. Experiment 33

NASA Technical Reports Server (NTRS)

Zhu, Ji-Xiang; Chaikin, P. M.; Li, Min; Russel, W. B.; Ottewill, R. H.; Rogers, R.; Meyer, W. V.

1998-01-01

Classical hard spheres have long served as a paradigm for our understanding of the structure of liquids, crystals, and glasses and the transitions between these phases. Ground-based experiments have demonstrated that suspensions of uniform polymer colloids are near-ideal physical realizations of hard spheres. However, gravity appears to play a significant and unexpected role in the formation and structure of these colloidal crystals. In the microgravity environment of the Space Shuttle, crystals grow purely via random stacking of hexagonal close-packed planes, lacking any of the face-centered cubic (FCC) component evident in crystals grown in 1 g beyond melting and allowed some time to settle. Gravity also masks 33-539 the natural growth instabilities of the hard sphere crystals which exhibit striking dendritic arms when grown in microgravity. Finally, high volume fraction "glass" samples which fail to crystallize after more than a year in 1 g begin nucleation after several days and fully crystallize in less than 2 weeks on the Space Shuttle.

Crystal Growth of Ternary Compound Semiconductors in Low Gravity Environment

NASA Technical Reports Server (NTRS)

Su, Ching-Hua

2014-01-01

A low gravity material experiment will be performed in the Material Science Research Rack (MSRR) on International Space Station (ISS). There are two sections of the flight experiment: (I) crystal growth of ZnSe and related ternary compounds, such as ZnSeS and ZnSeTe, by physical vapor transport (PVT) and (II) melt growth of CdZnTe by directional solidification. The main objective of the project is to determine the relative contributions of gravity-driven fluid flows to the compositional distribution, incorporation of impurities and defects, and deviation from stoichiometry observed in the grown crystals as results of buoyancy-driven convection and growth interface fluctuations caused by irregular fluid-flows on Earth. The investigation consists of extensive ground-based experimental and theoretical research efforts and concurrent flight experimentation. This talk will focus on the ground-based studies on the PVT crystal growth of ZnSe and related ternary compounds. The objectives of the ground-based studies are (1) obtain the experimental data and conduct the analyses required to define the optimum growth parameters for the flight experiments, (2) perfect various characterization techniques to establish the standard procedure for material characterization, (3) quantitatively establish the characteristics of the crystals grown on Earth as a basis for subsequent comparative evaluations of the crystals grown in a low-gravity environment and (4) develop theoretical and analytical methods required for such evaluations. ZnSe and related ternary compounds have been grown by vapor transport technique with real time in-situ non-invasive monitoring techniques. The grown crystals have been characterized extensively by various techniques to correlate the grown crystal properties with the growth conditions.

Magnetite Scavenging and the Buoyancy of Bubbles in Magmas

NASA Astrophysics Data System (ADS)

Gualda, G. A.; Ghiorso, M. S.

2005-12-01

It is generally assumed that when eruptions are triggered, magmas are bubble-free, and all the vesicularity observed in pumice is due to nucleation and growth during ascent. However, decompression experiments show that bubbles tend to nucleate on magnetite crystals at relatively low supersaturation, and there is convincing evidence that an exsolved gas phase was present during much of the evolution of the Bishop magma. The fate of pre-eruptive bubbles depends directly on their buoyancy, which can be strongly modified by the presence of crystals attached to the bubble-melt interface. That crystals tend to attach to bubbles is indicated by experiments and observations, and can be explained theoretically. Whether, however, crystals and bubbles can be held together by interface forces is yet uncertain, and we use the available knowledge on surface energies to explore this problem. We call adhesion energy the surface energy change due to attachment of a crystal to a bubble. We show that sticking a bubble to a mineral substrate is always energetically favored over keeping bubble and mineral separate. Because the adhesion energy is a strong function of the wetting angle, different minerals will be more strongly attached to bubbles than others. In particular, oxide minerals will attach to a given bubble much more strongly than any silicates. One interesting consequence of the attachment of grains to a bubble is that this can cause these bubble-crystal pairs to be neutrally buoyant, preventing bubble rise and crystal sinking. The criterion for buoyancy of a bubble-crystal pair can be calculated as the condition when the apparent weight of the crystal and the bubble are opposite and equal. If a bubble-mineral pair is to remain joined, the binding force has to be provided by the adhesion force, which is also a strong function of the wetting angle. Since the adhesion force is linear on R, and the buoyancy force is proportional to R cubed, there is a critical bubble radius below which the adhesion force will be strong enough to keep the pair together. Using the available experimental data, we show that crystals as large as 1 mm in diameter could be attached to bubbles and form neutrally buoyant pairs. The presence of multiple crystals in a single bubble would allow bubbles larger than the critical size to become neutrally buoyant. Under the limiting assumption that all magnetite crystals form neutrally buoyant pairs with bubbles, it is possible to compute the maximum gas volume fraction that can be stored as neutrally buoyant bubble-magnetite aggregates. The total abundance of magnetite is only ca. 0.1 vol. %, which yields maximum gas volume fractions on the order of 0.1-0.2 vol. %. About 2-3 vol % of gas can be accounted for if all minerals form neutrally-buoyant aggregates. These values are orders of magnitude lower than the abundance of exsolved gas inferred from melt inclusions in the Bishop magma. Nonetheless, our recent observation of one such aggregate in the early-erupted Bishop Tuff suggests that this is indeed a viable mechanism for storing exsolved gas in magmas. The inevitable conclusion is that a range of pre-eruptive bubbles existed, from magnetite-free, but only a very small fraction of them could have magnetite crystals attached to them. Our treatment shows that there should be an intrinsic association between magnetite crystals and bubbles. However, study our tomography datasets shows that most magnetite crystals are free of bubbles. Not only is this surprising; the puzzling conclusion is that nucleation away from crystals (homogeneous nucleation?) is favored over heterogeneous nucleation on crystal substrates.

Dose dependence of nano-hardness of 6H-SiC crystal under irradiation with inert gas ions

NASA Astrophysics Data System (ADS)

Yang, Yitao; Zhang, Chonghong; Su, Changhao; Ding, Zhaonan; Song, Yin

2018-05-01

Single crystal 6H-SiC was irradiated by inert gas ions (He, Ne, Kr and Xe ions) to various damage levels at room temperature. Nano-indentation test was performed to investigate the hardness change behavior with damage. The depth profile of nano-hardness for 6H-SiC decreased with increasing depth for both the pristine and irradiated samples, which was known as indentation size effect (ISE). Nix-Gao model was proposed to determine an asymptotic value of nano-hardness by taking account of ISE for both the pristine and irradiated samples. In this study, nano-hardness of the irradiated samples showed a strong dependence on damage level and showed a weak dependence on ions species. From the dependence of hardness on damage, it was found that the change of hardness demonstrated three distinguishable stages with damage: (I) The hardness increased with damage from 0 to 0.2 dpa and achieved a maximum of hardening fraction ∼20% at 0.2 dpa. The increase of hardness in this damage range was contributed to defects produced by ion irradiation, which can be described well by Taylor relation. (II) The hardness reduced rapidly with large decrement in the damage range from 0.2 to 0.5 dpa, which was considered to be from the covalent bond breaking. (III) The hardness reduced with small decrement in the damage range from 0.5 to 2.2 dpa, which was induced by extension of the amorphous layer around damage peak.

Age and petrology of the Tertiary As Sarat volcanic field, southwestern Saudi Arabia

USGS Publications Warehouse

du Bray, E.A.; Stoeser, D.B.; McKee, E.H.

1991-01-01

Harrat As Sarat forms the second smallest and southernmost of the basalt fields of western Saudi Arabia and is part of a voluminous Red Sea rift-related continental alkali basalt province. The rocks of the As Sarat were emplaced during the first stage of Red Sea rifting and represent the northernmost extension of the Tertiary Trap Series volcanics that occur mainly in the Yemen Arab Republic and Ethiopia. The field consists of up to 580 m of basalt flows, that are intruded by basaltic plugs, necks, minor dikes, and highly evolved peralkaline trachyte intrusions. K-Ar ages indicate that the As Sarat field formed between 31 and 22 Ma and contains an eruption hiatus of one million years that began about 25 Ma ago. Pre-hiatus flows are primarily hypersthene normative intersertal subalkaline basalt, whereas the majority of post-hiatus flows are nepheline normative alkali basalt and hawaiite with trachytic textures. Normative compositions of the basalts are consistent with their genesis by partial melting at varying depths. Trace element abundances in the basalt indicate that varying degrees of partial melting and fractional crystallization (or crystal accumulation) had major and minor roles, respectively, in development of compositional variation in these rocks. Modeling indicates that the pre-hiatus subalkaline basalts represent 8-10 percent mantle melting at depths of about 70 km and the post-hiatus alkali basalts represent 4-9 percent mantle melting at depths greater than 70 km. ?? 1991.

Photonic Crystals on the Wing

DTIC Science & Technology

2009-04-30

The Green Hairstreak butterfly has ventrally scales consisting of 3D gyroid domains acting as photonic crystals, which can be easily...study on the structural coloration of the Green Hairstreak , Callophrys rubi. Extensive experimental measurements have been complemented with three...colorations, produced by purely dielectric materials are widely encountered [1-3]. Famous examples are the metallic- green buprestid and golden scarab

Progress Toward a Monolithically Integrated Coherent Diode Laser Array.

DTIC Science & Technology

1981-02-20

eoCteehinique is uised extensively in fabricat ing MBR I iseor, ind pi~ rovide,, adidi t iooat infornation on the quality of the crystal. \\BR CAI FBR AI) \\R...crystals are then cleaned in hot isopropyl alcohol held in a vertical position by a glass holder submerged in isopropyl alcohol. They soak for about 1 hr

Amphibole-bearing multiphase solid inclusions in olivine, the Murotomisaki Gabbro, Southwest Japan: An evidence of hydrous flux melting

NASA Astrophysics Data System (ADS)

Hoshide, T.; Obata, M.

2009-12-01

The Murotomisaki Gabbro is a sill-like layered intrusion of up to 220m thickness exposed near Cape Muroto, Southwest Japan. Despite the small size of the intrusion, it contains well-developed centimeter- to meter-scale layered structures of modal variation of olivine, plagioclase and augite. Hoshide et al (2006a, b) identified the ’crystal accumulation zone’ (40m from the bottom) that was formed by gravitational settling of olivine crystals and the ’crystal growth zone’ (40-100m from the bottom), in which olivine crystals grew significantly. The fine-scale compositional layering is best developed in the ’crystal growth zone’. Amphibole-bearing multiphase solid inclusions (called ‘the amphibole-clot inclusions’) are common in olivine crystals from both the crystal accumulation- and the crystal growth zones. The amphibole clot inclusions show spherical or convex-polygonal shapes and are composed of pargasitic amphibole, biotite and orthopyroxene, with minor amounts of augite, apatite and opaque minerals. Plagioclase rarely occurs in the amphibole clot inclusions. Bulk chemical compositions of the inclusions, obtained from mineral microprobe analyses and modal composition, are characteristically high in MgO content (16-23 wt %) and they roughly lie between presumable fractionated melt compositions and olivine compositions. From observations above, it is likely that amphibole clot inclusions are of melt origin, which had formed from some hydrous melts probably entrapped in growing olivine crystals. However, it may be difficult to explain both the very magnesian nature of the inclusion and absence of plagioclase in the inclusion by the crystallization of the normal hydrous basaltic melt. The difficulty may be resolved if we suppose, for a trapped melt composition, a more magnesian (i.e., picritic) composition. The highly magnesian nature of the amphibole clot inclusions may suggest that significant amount of olivine component had been added to fractionated melts that was once equilibrated with olivine. Such addition of olivine component may be realized by dissolution of olivine, which may be induced by introduction of water from the lower horizons of the crystallization boundary layer (e.g., McBirney, 1987). Amphibole clot inclusion in olivine is, therefore, considered to be a new evidence for dissolution of olivine by hydrous fluxing.

Zn isotope fractionation in the komatiitic and tholeiitic lava flows of Fred's flow and Theo's flow (Ontario, Canada)

NASA Astrophysics Data System (ADS)

Mattielli, N. D.; Haenecour, P.; Debaille, V.

2010-12-01

Komatiites are subvolcanic or volcanic ultramafic rocks characterized by a high MgO content (>18 wt%) usually but not systematically associated to a spinifex texture. Komatiites are nearly exclusively Archean in age and essentially found in the greenstone belts of the oldest cratons, although some rare Proterozoic and Cretaceous examples are also known. Komatiitic flows are commonly associated with tholeiitic lavas, which have many petrological, textural and geochemical similarities with komatiites. We present new high-precision MC-ICPMS Zinc isotopic data for the komatiitic lavas of Fred’s flow and the associated tholeiitic lavas of Theo’s flow from Munro Township in the 2.7 Ga Abitibi greenstone belt (Ontario, Canada). Zinc isotopes show a significant shift between Fred’s flow (mean δ66Zn = +0.30±0.04‰ (2SD)) and Theo’s flow samples (mean δ66Zn = +0.39±0.03‰ (1)). In addition, the two flows show a systematic shift in δ66Zn between the ultrabasic level at the bottom of the sequence (= +0.51± 0.04‰ and +0.47±0.04‰ for Fred’s Flow and Theo’s Flow, respectively) and the rest of the pile (Δ = 0.21±0.01‰). According to the literature, processes of secondary alteration may cause Zn isotope fractionation. However, petrographic data indicate a slight alteration fingerprint while the geochemical study (whole rock and in-situ) shows no remobilization of HFSE and REE by secondary alteration (low-grade metamorphism and/or hydrothermal alteration). In addition, if similar levels of alteration affected the two lava flows, the alteration process cannot explain the difference of δ66Zn between Fred’s and Theo’s flows. Alternatively, this isotopic difference can be interpreted as reflecting either source effects or mineral fractionation related to spinel crystallization. The correlation between the δ66Zn values and the Cr bulk concentrations may suggest fractionation effects of Zn isotopes by the crystallization of spinel minerals. However, the conditions and the processes implying Zn isotopic fractionation during the crystallization of spinel minerals are still not much studied. Isotopic fractionation related to source effects cannot also be excluded. This latter hypothesis implies that Fred’s flow and Theo’s flow formed from two geochemical or mineralogical different mantle sources. While the geochemical data do not support or invalidate this second hypothesis, two different sources may explain the difference between the two lava flows; however, it cannot account for the isotopic variations observed at the ultrabasic levels. In conclusion, the role of mineralogy either at the origin or during the crystallization evolution should be investigated for a better understanding of Zn isotope fractionation in the mantle. (1): To validate the quality of isotopic analyses, reference materials BCR-1(basalt) (δ66Zn = +0.33±0.03‰) and HRM-27(gabbro) (+0.17±0.01‰) (n=3) have been measured.

Extension of supercontinuum spectrum, generated in polarization-maintaining photonic crystal fiber, using chirped femtosecond pulses

NASA Astrophysics Data System (ADS)

Vengelis, Julius; Jarutis, Vygandas; Sirutkaitis, Valdas

2018-01-01

We present results of experimental and numerical investigation of supercontinuum (SC) generation in polarization-maintaining photonic crystal fiber (PCF) using chirped femtosecond pulses. The initial unchirped pump pulse source was a mode-locked Yb:KGW laser generating 52-nJ energy, 110-fs duration pulses at 1030 nm with a 76-MHz repetition rate. The nonlinear medium was a 32-cm-long polarization-maintaining PCF manufactured by NKT Photonics A/S. We demonstrated the influence of pump pulse chirp on spectral characteristics of a SC. We showed that by chirping pump pulses positively or negatively one can obtain a broader SC spectrum than in the case of unchirped pump pulses at the same peak power. Moreover, the extension can be controlled by changing the amount of pump pulse chirp. Numerical simulation results also indicated that pump pulse chirp yields an extension of SC spectrum.

Alpha-enolase on apical surface of renal tubular epithelial cells serves as a calcium oxalate crystal receptor

NASA Astrophysics Data System (ADS)

Fong-Ngern, Kedsarin; Thongboonkerd, Visith

2016-10-01

To search for a strategy to prevent kidney stone formation/recurrence, this study addressed the role of α-enolase on apical membrane of renal tubular cells in mediating calcium oxalate monohydrate (COM) crystal adhesion. Its presence on apical membrane and in COM crystal-bound fraction was confirmed by Western blotting and immunofluorescence staining. Pretreating MDCK cells with anti-α-enolase antibody, not isotype-controlled IgG, dramatically reduced cell-crystal adhesion. Immunofluorescence staining also confirmed the direct binding of purified α-enolase to COM crystals at {121} > {100} > {010} crystal faces. Coating COM crystals with urinary proteins diminished the crystal binding capacity to cells and purified α-enolase. Moreover, α-enolase selectively bound to COM, not other crystals. Chemico-protein interactions analysis revealed that α-enolase interacted directly with Ca2+ and Mg2+. Incubating the cells with Mg2+ prior to cell-crystal adhesion assay significantly reduced crystal binding on the cell surface, whereas preincubation with EDTA, a divalent cation chelator, completely abolished Mg2+ effect, indicating that COM and Mg2+ competitively bind to α-enolase. Taken together, we successfully confirmed the role of α-enolase as a COM crystal receptor to mediate COM crystal adhesion at apical membrane of renal tubular cells. It may also serve as a target for stone prevention by blocking cell-crystal adhesion and stone nidus formation.

Fourier transform imaging of impurities in the unit cells of crystals: Mn in GaAs

NASA Astrophysics Data System (ADS)

Lee, T.-L.; Bihler, C.; Schoch, W.; Limmer, W.; Daeubler, J.; Thieß, S.; Brandt, M. S.; Zegenhagen, J.

2010-06-01

The lattice sites of Mn in ferromagnetic (Ga,Mn)As thin films were imaged using the x-ray standing wave technique. The model-free images, obtained straightforwardly by Fourier inversion, disclose immediately that the Mn mostly substitutes the Ga with a small fraction residing on minority sites. The images further reveal variations in the Mn concentrations of the different sites upon post-growth treatments. Subsequent model refinement based on the directly reconstructed images resolves with high precision the complete Mn site distributions. It is found that post-growth annealing increases the fraction of substitutional Mn at the expense of interstitial Mn whereas hydrogenation has little influence on the Mn site distribution. Our study offers an element-specific high-resolution imaging approach for accurately determining the detailed site distributions of dilute concentrations of atoms in crystals.

Fractional Brownian motion run with a multi-scaling clock mimics diffusion of spherical colloids in microstructural fluids.

PubMed

Park, Moongyu; Cushman, John Howard; O'Malley, Dan

2014-09-30

The collective molecular reorientations within a nematic liquid crystal fluid bathing a spherical colloid cause the colloid to diffuse anomalously on a short time scale (i.e., as a non-Brownian particle). The deformations and fluctuations of long-range orientational order in the liquid crystal profoundly influence the transient diffusive regimes. Here we show that an anisotropic fractional Brownian process run with a nonlinear multiscaling clock effectively mimics this collective and transient phenomenon. This novel process has memory, Gaussian increments, and a multiscale mean square displacement that can be chosen independently from the fractal dimension of a particle trajectory. The process is capable of modeling multiscale sub-, super-, or classical diffusion. The finite-size Lyapunov exponents for this multiscaling process are defined for future analysis of related mixing processes.

Rigid Amorphous Fraction in PLA Electrospun Fibers

NASA Astrophysics Data System (ADS)

Cebe, Peggy; Ma, Qian; Simona Cozza, Erika; Pyda, Marek; Mao, Bin; Zhu, Yazhe; Monticelli, Orietta

2013-03-01

Electrospun fibers of poly(lactic acid) (PLA) were formed by adopting a high-speed rotating wheel as the counter-electrode. The molecular orientation, crystallization mechanism, and phase structure and transitions of the aligned ES fibers were investigated. Using thermal analysis and wide angle X-ray scattering (WAXS), we evaluated the confinement that exists in as-spun amorphous, and heat-treated semicrystalline, fibers. Differential scanning calorimetry confirmed the existence of a constrained amorphous phase in as-spun aligned fibers, without the presence of crystals or fillers to serve as fixed physical constraints. Using WAXS, for the first time the mesophase fraction, consisting of oriented amorphous PLA chains, was quantitatively characterized in nanofibers. The authors acknowledge support from the National Science Foundation, Polymers Program under grant DMR-0602473. ESC acknowledges a Ph.D. grant supported by Italian Ministry of Education and Scientific Research.

Polymeric proanthocyanidins from the bark of Hamamelis virginiana.

PubMed

Dauer, A; Rimpler, H; Hensel, A

2003-01-01

Polymeric proanthocyanidins were isolated from the bark of Hamamelis virginiana L. in yields of about 5 %. Fractionation yielded fractions with similar structures but different molecular weights with DP between 17-29 (thiolysis) and 11-20 (GPC). Polymers were composed predominantly of epicatechin and epigallocatechin as chain extension units at ratio of about 1.3:1. Terminal chain units were catechin (approximately 95 %) and gallocatechin (approximately 5 %). All chain extension units were completely galloylated at position O-3, while chain terminating units were not galloylated. Predominant interflavan linkages were 4 --> 8-bonds.

Petrological constraints on the high-Mg basalts from Capo Marargiu (Sardinia, Italy): Evidence of cryptic amphibole fractionation in polybaric environments

NASA Astrophysics Data System (ADS)

Tecchiato, Vanni; Gaeta, Mario; Mollo, Silvio; Scarlato, Piergiorgio; Bachmann, Olivier; Perinelli, Cristina

2018-01-01

This study deals with the textural and compositional characteristics of the calc-alkaline stratigraphic sequence from Capo Marargiu Volcanic District (CMVD; Sardinia island, Italy). The area is dominated by basaltic to intermediate hypabyssal (dikes and sills) and volcanic rocks (lava flows and pyroclastic deposits) emplaced during the Oligo-Miocene orogenic magmatism of Sardinia. Interestingly, a basaltic andesitic dome hosts dark-grey, crystal-rich enclaves containing up 50% of millimetre- to centimetre-sized clinopyroxene and amphibole crystals. This mineral assemblage is in equilibrium with a high-Mg basalt recognised as the parental magma of the entire stratigraphic succession at CMVD. Analogously, centimetre-sized clots of medium- and coarse-grained amphibole + plagioclase crystals are entrapped in andesitic dikes that ultimately intrude the stratigraphic sequence. Amphibole-plagioclase cosaturation occurs at equilibrium with a differentiated basaltic andesite. Major and trace element modelling indicates that the evolutionary path of magma is controlled by a two-step process driven by early olivine + clinopyroxene and late amphibole + plagioclase fractionation. In this context, enclaves represent parts of a cumulate horizon segregated at the early stage of differentiation of the precursory high-Mg basalt. This is denoted by i) resorption effects and sharp transitions between Mg-rich and Mg-poor clinopyroxenes, indicative of pervasive dissolution phenomena followed by crystal re-equilibration and overgrowth, and ii) reaction minerals found in amphibole coronas formed at the interface with more differentiated melts infiltrating within the cumulate horizon, and carrying the crystal-rich material with them upon eruption. Coherently, the mineral chemistry and phase relations of enclaves indicate crystallisation in a high-temperature, high-pressure environment under water-rich conditions. On the other hand, the upward migration and subsequent fractionation of the residual basaltic andesite in a shallower, colder, and hydrous region of the CMVD plumbing system lead to the formation of the amphibole-plagioclase crystal clots finally entrained by the andesitic dikes. Indeed, phenocrysts from these more evolved products record the final crystallisation path of magma during ascent towards the surface. Magma decompression and volatile loss cause the formation of amphibole reaction coronas and the crystallisation of a more sodic plagioclase in equilibrium with basaltic andesitic to andesitic melts. The bulk-rock geochemical signature of these products testifies to open-system, polybaric magma dynamics, accounting for variable degrees of crustal assimilation of the Hercynian basement of Sardinia.

Exploring the folding pattern of a polymer chain in a single crystal by combining single-molecule force spectroscopy and steered molecular dynamics simulations.

PubMed

Song, Yu; Feng, Wei; Liu, Kai; Yang, Peng; Zhang, Wenke; Zhang, Xi

2013-03-26

Understanding the folding pattern of a single polymer chain within its single crystal will shed light on the mechanism of crystallization. Here, we use the combined techniques of atomic force microscopy (AFM)-based single-molecule force spectroscopy (SMFS) and steered molecular dynamics (SMD) simulations to study the folding pattern of a polyethylene oxide (PEO) chain in its single crystal. Our results show that the folding pattern of a PEO chain in the crystal formed in dilute solution follows the adjacent re-entry folding model. While in the crystal obtained from the melt, the nonadjacent folding with large and irregular loops contributes to big force fluctuations in the force-extension curves. The method established here can offer a novel strategy to directly unravel the chain-folding pattern of polymer single crystals at single-molecule level.

Crystallization of Deformable Spherical Colloids

NASA Astrophysics Data System (ADS)

Batista, Vera M. O.; Miller, Mark A.

2010-08-01

We introduce and characterize a first-order model for a generic class of colloidal particles that have a preferred spherical shape but can undergo deformations while always maintaining hard-body interactions. The model consists of hard spheres that can continuously change shape at fixed volume into prolate or oblate ellipsoids of revolution, subject to an energetic penalty. The severity of this penalty is specified by a single parameter that determines the flexibility of the particles. The deformable hard spheres crystallize at higher packing fractions than rigid hard spheres, have a narrower solid-fluid coexistence region and can reach high densities by a second transition to an orientationally ordered crystal.

Lattice-Rotation Vortex at the Charged Monoclinic Domain Boundary in a Relaxor Ferroelectric Crystal

NASA Astrophysics Data System (ADS)

Shao, Yu-Tsun; Zuo, Jian-Min

2017-04-01

We present evidence of lattice-rotation vortices having an average radius of ˜7 nm at the ferroelectric domain boundary of (1 -x )Pb (Zn1 /3Nb2 /3)O3-xPbTiO3 (x =0.08 ). Maps of crystal orientations and domain symmetry breaking are obtained using scanning convergent beam electron diffraction, which show fractional rotation vortices near the 50° monoclinic domain walls. The merging of 2D and 1D topological defects is consistent with inhomogeneous boundary charge and expected to have a large impact on the domain-switching mechanisms in relaxor ferroelectric crystals and ferroelectric devices.

Crystal Growth of ZnSe and Related Ternary Compound Semiconductors by Vapor Transport

NASA Technical Reports Server (NTRS)

2003-01-01

The objective of the project is to determine the relative contributions of gravity-driven fluid flows to the compositional distribution, incorporation of impurities and defects, and deviation from stoichiometry observed in the crystals grown by vapor transport as results of buoyancy-driven convection and growth interface fluctuations caused by irregular fluid-flows. ZnSe and related ternary compounds, such as ZnSeS and ZnSeTe, were grown by vapor transport technique with real time in situ non-invasive monitoring techniques. The grown crystals were characterized extensively to correlate the grown crystal properties with the growth conditions. Significant effects of gravity vector orientation on the growth crystal morphology and point defect distribution were observed.

Cobalt and scandium partitioning versus iron content for crystalline phases in ultramafic nodules

USGS Publications Warehouse

Glassley, W.E.; Piper, D.Z.

1978-01-01

Fractionation of Co and Sc between garnets, olivines, and clino- and orthopyroxenes, separated from a suite of Salt Lake Crater ultramafic nodules that equilibrated at the same T and P, is strongly dependent on Fe contents. This observation suggests that petrogenetic equilibrium models of partial melting and crystal fractionation must take into account effects of magma composition, if they are to describe quantitatively geochemical evolutionary trends. ?? 1978.

Purification, crystallization and preliminary X-ray analysis of urease from pigeon pea (Cajanus cajan)

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

Balasubramanian, Anuradha; Ponnuraj, Karthe, E-mail: pkarthe@hotmail.com

Urease from pigeon pea was purified and crystallized and X-ray diffraction data were collected at 2.5 Å resolution. Urease is a seed protein that is common to most Leguminosae. It also occurs in many bacteria, fungi and several species of yeast. Urease catalyzes the hydrolysis of urea to ammonia and carbon dioxide, thus allowing organisms to use exogenous and internally generated urea as a nitrogen source. Urease from pigeon pea seeds has been purified to electrophoretic homogeneity using a series of steps involving ammonium sulfate fractionation, acid precipitation, ion-exchange and size-exclusion chromatography techniques. The pigeon pea urease was crystallized andmore » the resulting crystals diffracted to 2.5 Å resolution. The crystals belong to the rhombohedral space group R32, with unit-cell parameters a = b = 176.29, c = 346.44 Å.« less

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

Cebe, Peggy; Partlow, Benjamin P.; Kaplan, David L.

Using fast scanning calorimetry (FSC), we investigated the glass transition and crystal melting of samples of B. mori silk fibroin containing Silk I and/or Silk II crystals. Due to the very short residence times at high temperatures during such measurements, thermal decomposition of silk protein can be significantly suppressed. FSC was performed at 2000 K/s using the Mettler Flash DSC1 on fibroin films with masses around 130–270 ng. Films were prepared with different crystalline fractions (ranging from 0.26 to 0.50) and with different crystal structures (Silk I, Silk II, or mixed) by varying the processing conditions. These included water annealingmore » at different temperatures, exposure to 50% MeOH in water, or autoclaving. The resulting crystal structure was examined using wide angle X-ray scattering. Degree of crystallinity was evaluated from Fourier transform infrared (FTIR) spectroscopy and from analysis of the heat capacity increment at the glass transition temperature. Silk fibroin films prepared by water annealing at 25 °C were the least crystalline and had Silk I structure. FTIR and FSC studies showed that films prepared by autoclaving or 50% MeOH exposure were the most crystalline and had Silk II structure. Intermediate crystalline fraction and mixed Silk I/Silk II structures were found in films prepared by water annealing at 37 °C. FSC results indicate that Silk II crystals exhibit endotherms of narrower width and have higher mean melting temperature Tm(II) = 351 ± 2.6 °C, compared to Silk I crystals which melt at Tm(I) = 292 ± 3.8 °C. Films containing mixed Silk I/Silk II structure showed two clearly separated endothermic peaks. Evidence suggests that the two types of crystals melt separately and do not thermally interconvert on the extremely short time scale (0.065 s between onset and end of melting) of the FSC experiment.« less

Chemical consequences of compaction within the freezing front of a crystallizing magma ocean

NASA Astrophysics Data System (ADS)

Hier-Majumder, S.; Hirschmann, M. M.

2013-12-01

The thermal and compositional evolution of planetary magma oceans have profound influences on the early development and differentiation of terrestrial planets. During crystallization, rejection of elements incompatible in precipitating solids leads to petrologic and geochemical planetary differentiation, including potentially development of a compositionally stratified early mantle and evolution of thick overlying atmospheres. In cases of extremely efficient segregation of melt and crystals, solidified early mantles can be nearly devoid of key incompatible species including heat-producing (U, Th, K) and volatile (H,C,N,& noble gas) elements. A key structural component of a crystallizing magma ocean is the partially molten freezing front. The dynamics of this region influences the distribution of incompatible elements between the earliest mantle and the initial surficial reservoirs. It also can be the locus of heating owing to the dissipation of large amounts of tidal energy potentially available from the early Moon. The dynamics are influenced by the solidification rate, which is coupled to the liberation of volatiles owing to the modulating greenhouse effects in the overlying thick atmosphere. Compaction and melt retention in the freezing front of a magma ocean has received little previous attention. While the front advances during the course of crystallization, coupled conservation of mass, momentum, and energy within the front controls distribution and retention of melt within this layer. Due to compaction within this layer, melt distribution is far from uniform, and the fraction of melt trapped within this front depends on the rate of freezing of the magma ocean. During phases of rapid freezing, high amount of trapped melt within the freezing front retains a larger quantity of dissolved volatiles and the reverse is true during slow periods of crystallization. Similar effects are known from inferred trapped liquid fractions in layered mafic intrusions. Here we develop a simple 1-D model of melt retention in the freezing front of a crystallizing magma ocean, and apply it to the thermal and chemical evolution of the early Earth.

Predicting the mineral composition of dust aerosols - Part 1: Representing key processes

NASA Astrophysics Data System (ADS)

Perlwitz, J. P.; Pérez García-Pando, C.; Miller, R. L.

2015-02-01

Soil dust aerosols created by wind erosion are typically assigned globally uniform physical and chemical properties within Earth system models, despite known regional variations in the mineral content of the parent soil. Mineral composition of the aerosol particles is important to their interaction with climate, including shortwave absorption and radiative forcing, nucleation of cloud droplets and ice crystals, coating by heterogeneous uptake of sulfates and nitrates, and atmospheric processing of iron into bioavailable forms that increase the productivity of marine phytoplankton. Here, aerosol mineral composition is derived by extending a method that provides the composition of a wet-sieved soil. The extension accounts for measurements showing significant differences between the mineral fractions of the wet-sieved soil and the resulting aerosol concentration. For example, some phyllosilicate aerosols are more prevalent at silt sizes, even though they are nearly absent in a soil whose aggregates are dispersed by wet sieving during analysis. We reconstruct the undispersed size distribution of the original soil that is subject to wind erosion. An empirical constraint upon the relative emission of clay and silt is applied that further differentiates the soil and aerosol mineral composition. In addition, a method is proposed for mixing minerals with small impurities composed of iron oxides. These mixtures are important for transporting iron far from the dust source, because pure iron oxides are more dense and vulnerable to gravitational removal than most minerals comprising dust aerosols. A limited comparison to measurements from North Africa shows that the extension brings the model into better agreement, consistent with a more extensive comparison to global observations as well as measurements of elemental composition downwind of the Sahara, as described in companion articles.

Formation of Intermediate Plutonic Rocks by Magma Mixing: the Shoshonite Suite of Timna, Southern Israel.

NASA Astrophysics Data System (ADS)

Fox, S.; Katzir, Y.

2017-12-01

In magmatic series considered to form by crystal fractionation intermediate rocks are usually much less abundant than expected. Yet, intermediate plutonic rocks, predominantly monzodiorites, are very abundant in the Neoproterozoic Timna igneous complex, S. Israel. A previously unnoticed plutonic shoshonitic suite was recently defined and mapped in Timna (Litvinovsky et al., 2015). It mostly comprises intermediate rocks in a seemingly 'continuous' trend from monzodiorite through monzonite to quartz syenite. Macroscale textures including gradational boundaries of mafic and felsic rocks and MME suggest that magma mixing is central in forming intermediate rocks in Timna. Our petrographic, microtextural and mineral chemistry study delineates the mode of incipient mixing, ultimate mingling and crystal equilibration in hybrid melts. An EMP study of plagioclase from rocks across the suite provides a quantitative evaluation of textures indicative of magma mixing/mingling, including recurrent/patchy zoning, Ca spike, boxy/sponge cellular texture and anti-Rapakivi texture. Each texture has an affinity to a particular mixing region. A modal count of these textures leads to a kinetic mixing model involving multi temporal and spatial scales necessary to form the hybrid intermediate rocks. A `shell'-like model for varying degrees of mixing is developed with the more intensive mixing at the core and more abundant felsic and mafic end-members towards the outer layer. REE patterns in zircon shows that it originated from both mafic and felsic parent melts. Whole rock Fe vs Sr plot suggests a two-stage mixing between the monzogabbro and quartz-syenite producing first mesocratic syenite, and subsequent mixing with a fractionating monzogabbro resulting in monzonitic compositions. A fractionating monzogabbro intruded into a syenitic melt sequentially. While slowly cooling, the monzogabbro heated the immediate syenitic melt, lowering the viscosity and rheological obstruction to overturn the boundary, and thus facilitated mixing. Increasing melt hybridization, tandem with crystallization, produced mixing textures in the turbulent crystal mush zone, synchronously with `pure end-member' crystallization. As a result, a large volume of intermediate rock was created through a hybridization process.

Variations of trace element concentration of magnetite and ilmenite from the Taihe layered intrusion, Emeishan large igneous province, SW China: Implications for magmatic fractionation and origin of Fe-Ti-V oxide ore deposits

NASA Astrophysics Data System (ADS)

She, Yu-Wei; Song, Xie-Yan; Yu, Song-Yue; He, Hai-Long

2015-12-01

In situ LA-ICP-MS trace elemental analysis has been applied to magnetite and ilmenite of the Taihe layered intrusion, Emeishan large igneous province, SW China, in order to understand better fractionation processes of magma and origin of Fe-Ti-V oxide ore deposits. The periodic reversals in Mg, Ti, Mn in magnetite and Mg, Sc in ilmenite are found in the Middle Zone of the intrusion and agree with fractionation trends as recorded by olivine (Fo), plagioclase (An) and clinopyroxene (Mg#) compositions. These suggest the Taihe intrusion formed from open magma chamber processes in a magma conduit with multiple replenishments of more primitive magmas. The V and Cr of magnetite are well correlated with V and Cr of clinopyroxene indicating that they became liquidus phases almost simultaneously at an early stage of magma evolution. Ilmenite from the Middle and Upper Zones shows variable Cr, Ni, V, Mg, Nb, Ta and Sc contents indicating that ilmenite at some stratigraphic levels crystallized slightly earlier than magnetite and clinopyroxene. The early crystallization of magnetite and ilmenite is the result of the high FeOt and TiO2 contents in the parental magma. The ilmenite crystallization before magnetite in the Middle and Upper Zones can be attributed to higher TiO2 content of the magma due to the remelting of pre-existing ilmenite in a middle-level magma chamber. Compared to the coeval high-Ti basalts, the relatively low Zr, Hf, Nb and Ta contents in both magnetite and ilmenite throughout the Taihe intrusion indicate that they crystallized from Fe-Ti-(P)-rich silicate magmas. Positive correlations of Ti with Mg, Mn, Sc and Zr of magnetite, and Zr with Sc, Hf and Nb of ilmenite also suggest that magnetite and ilmenite crystallized continuously from the homogeneous silicate magma rather than an immiscible Fe-rich melt. Therefore, frequent replenishments of Fe-Ti-(P)-rich silicate magma and gravitational sorting and settling are crucial for the formation the massive and apatite-rich disseminated ores in the Lower and Middle Zones of the Taihe intrusion.

In Situ Time-Resolved Measurements of Extension Twinning During Dynamic Compression of Polycrystalline Magnesium

NASA Astrophysics Data System (ADS)

Hustedt, C. J.; Lambert, P. K.; Kannan, V.; Huskins-Retzlaff, E. L.; Casem, D. T.; Tate, M. W.; Philipp, H. T.; Woll, A. R.; Purohit, P.; Weiss, J. T.; Gruner, S. M.; Ramesh, K. T.; Hufnagel, T. C.

2018-04-01

We report in situ time-resolved measurements of the dynamic evolution of the volume fraction of extension twins in polycrystalline pure magnesium and in the AZ31B magnesium alloy, using synchrotron x-ray diffraction during compressive loading at high strain rates. The dynamic evolution of the twinning volume fraction leads to a dynamic evolution of the texture. Although both the pure metal and the alloy had similar initial textures, we observe that the evolution of texture is slower in the alloy. We also measured the evolution of the lattice strains in each material during deformation which, together with the twin volume fractions, allows us to place some constraints on the relative contributions of dislocation-based slip and deformation twinning to the overall plastic deformation during the dynamic deformations.

Chemistry of the subalkalic silicic obsidians

USGS Publications Warehouse

MacDonald, Ray; Smith, Robert L.; Thomas, John E.

1992-01-01

Nonhydrated obsidians are quenched magmatic liquids that record in their chemical compositions details of the tectonic environment of formation and of the differentiation mechanisms that affected their subsequent evolution. This study attempts to analyze, in terms of geologic processes, the compositional variations in the subalkalic silicic obsidians (Si02≥70 percent by weight, molecular (Na2O+K20)>Al2O3). New major- and trace-element determinations of 241 samples and a compilation of 130 published major-element analyses are reported and interpreted. Obsidians from five different tectonic settings are recognized: (1) primitive island arcs, (2) mature island arcs, (3) continental margins, (4) continental interiors, and (5) oceanic extensional zones. Tectonomagmatic discrimination between these groups is successfully made on Nb-Ta, Nb-FeOt and Th-Hf-Ta plots, and compositional ranges and averages for each group are presented. The chemical differences between groups are related to the type of crust in which magmas were generated. With increasingly sialic (continental type) crust, the obsidians show overall enrichment in F, Be, Li, Mo, Nb, Rb, Sn, Ta, U, W, Zn, and the rare-earth elements, and depletion in Mg, Ca, Ba, Co, Sc, Sr, and Zr. They become more potassic, have higher Fe/Mg and F/Cl ratios, and lower Zr/Hf, Nb/Ta, and Th/U ratios. Higher values of total rare-earth elements are accompanied by light rare-earth-element enrichment and pronounced negative Eu anomalies. An attempt is made to link obsidian chemistry to genetic mechanlism. Two broad groups of rocks are distinguished: one generated where crystal-liquid processes dominated (CLPD types), which are the products of crustal anatexis, possibly under conditions of low halogen fugacity, ± crystal fractionation ± magma mixing; and a second group represented by rocks formed in the upper parts of large magma chambers by interplays of crystal fractionation, volatile transfer, magma mixing, and possibly various liquid-state differentiation mechanisms, or in other words a complex interaction of petrogenetic processes (CIPP types). Such rocks may also form by volatile-fluxed partial melting of the wallrocks, and subsequent mixing into the magma reservoir. Compositional ranges and averages for CLPD and CIPP obsidians are given. It is shown by analogy with well-documented, zoned ash-flow ruffs that obsidians fractionated by CIPP have very low Mg, P, Ba, and Sr contents, flat rare-earth-element patterns with extensive Eu anomalies, low K/Rb and Zr/Nb ratios, and relatively high Na2O/K2O ratios. There is, however, considerable compositional overlap between CLPD and CIPP obsidians. The effects of magma mixing, assimilation, and vapor-phase transport in producing compositional variations in the obsidians are briefly assessed. The geochemistry of the subalkalic silicic obsidians is described on an element-by-element basis, in order to provide a database for silicic magma compositions that will hopefully contribute to studies of granitic rocks. Attempts are also made to isolate the geochemical effects of tectonic environment and genetic mechanism for each element, by comparison with data from crystal-liquid equilibria-controlled systems, from ash-flow sheets zoned by CIPP, and from mixed-magma series. A final tabulation relates the complexities of obsidian geochemistry to all the tectonic and genetic variables.

Purification, crystallization and preliminary X-ray analysis of urease from pigeon pea (Cajanus cajan)

PubMed Central

Balasubramanian, Anuradha; Ponnuraj, Karthe

2008-01-01

Urease is a seed protein that is common to most Leguminosae. It also occurs in many bacteria, fungi and several species of yeast. Urease catalyzes the hydrolysis of urea to ammonia and carbon dioxide, thus allowing organisms to use exogenous and internally generated urea as a nitrogen source. Urease from pigeon pea seeds has been purified to electrophoretic homogeneity using a series of steps involving ammonium sulfate fractionation, acid precipitation, ion-exchange and size-exclusion chromatography techniques. The pigeon pea urease was crystallized and the resulting crystals diffracted to 2.5 Å resolution. The crystals belong to the rhombohedral space group R32, with unit-cell parameters a = b = 176.29, c = 346.44 Å. PMID:18607103

Slow light generation in single-mode rectangular core photonic crystal fiber

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

Yadav, Sandeep; Saini, Than Singh; Kumar, Ajeet, E-mail: ajeetdph@gmail.com

2016-05-06

In this paper, we have designed and analyzed a rectangular core photonic crystal fiber (PCF) in Tellurite material. For the designed photonics crystal fiber, we have calculated the values of confinement loss and effective mode area for different values of air filling fraction (d/Λ). For single mode operation of the designed photonic crystal fiber, we have taken d/Λ= 0.4 for the further calculation of stimulated Brillouin scattering based time delay. A maximum time delay of 158 ns has been achieved for input pump power of 39 mW. We feel the detailed theoretical investigations and simulations carried out in the study have themore » potential impact on the design and development of slow light-based photonic devices.« less

Nucleation and Growth of Crystalline Grains in RF-Sputtered TiO 2 Films

DOE PAGES

Johnson, J. C.; Ahrenkiel, S. P.; Dutta, P.; ...

2009-01-01

Amore » morphous TiO 2 thin films were radio frequency sputtered onto siliconmonoxide and carbon support films on molybdenum transmission electron microscope (TEM) grids and observed during in situ annealing in a TEM heating stage at 250 ∘ C. The evolution of crystallization is consistent with a classical model of homogeneous nucleation and isotropic grain growth. The two-dimensional grain morphology of the TEM foil allowed straightforward recognition of amorphous and crystallized regions of the films, for measurement of crystalline volume fraction and grain number density. By assuming that the kinetic parameters remain constant beyond the onset of crystallization, the final average grain size was computed, using an analytical extrapolation to the fully crystallized state. Electron diffraction reveals a predominance of the anatase crystallographic phase.« less

Effects of Lipid-Analog Detergent Solubilization on the Functionality and Lipidic Cubic Phase Mobility of the Torpedo californica Nicotinic Acetylcholine Receptor

PubMed Central

Padilla-Morales, Luis F.; Morales-Pérez, Claudio L.; De La Cruz-Rivera, Pamela C.; Asmar-Rovira, Guillermo; Báez-Pagán, Carlos A.

2011-01-01

Over the past three decades, the Torpedo californica nicotinic acetylcholine receptor (nAChR) has been one of the most extensively studied membrane protein systems. However, the effects of detergent solubilization on nAChR stability and function are poorly understood. The use of lipid-analog detergents for nAChR solubilization has been shown to preserve receptor stability and functionality. The present study used lipid-analog detergents from phospholipid-analog and cholesterol-analog detergent families for solubilization and affinity purification of the receptor and probed nAChR ion channel function using planar lipid bilayers (PLBs) and stability using analytical size exclusion chromatography (A-SEC) in the detergent-solubilized state. We also examined receptor mobility on the lipidic cubic phase (LCP) by measuring the nAChR mobile fraction and diffusion coefficient through fluorescence recovery after photobleaching (FRAP) experiments using lipid-analog and non-lipid-analog detergents. Our results show that it is possible to isolate stable and functional nAChRs using lipid-analog detergents, with characteristic ion channel currents in PLBs and minimal aggregation as observed in A-SEC. Furthermore, fractional mobility and diffusion coefficient values observed in FRAP experiments were similar to the values observed for these parameters in the recently LCP-crystallized β2-adrenergic receptor. The overall results show that phospholipid-analog detergents with 16 carbon acyl-chains support nAChR stability, functionality and LCP mobility. PMID:21922299

Petrogenesis and tectonic implications of Late Carboniferous A-type granites and gabbronorites in NW Iran: Geochronological and geochemical constraints

NASA Astrophysics Data System (ADS)

Moghadam, Hadi Shafaii; Li, Xian-Hua; Ling, Xiao-Xiao; Stern, Robert J.; Santos, Jose F.; Meinhold, Guido; Ghorbani, Ghasem; Shahabi, Shirin

2015-01-01

Carboniferous igneous rocks constitute volumetrically minor components of Iranian crust but preserve important information about the magmatic and tectonic history of SW Asia. Ghushchi granites and gabbronorites in NW Iran comprise a bimodal magmatic suite that intruded Ediacaran-Cambrian gneiss and are good representatives of carboniferous igneous activity. Precise SIMS U-Pb zircon ages indicate that the gabbronorites and granites were emplaced synchronously at ~ 320 Ma. Ghushchi granites show A-type magmatic affinities, with typical enrichments in alkalis, Ga, Zr, Nb and Y, depletion in Sr and P and fractionated REE patterns showing strong negative Eu anomalies. The gabbronorites are enriched in LREEs, Nb, Ta and other incompatible trace elements, and are similar in geochemistry to OIB-type rocks. Granites and gabbronorites have similar εNd(t) (+ 1.3 to + 3.4 and - 0.1 to + 4.4, respectively) and zircon εHf(t) (+ 1.7 to + 6.2 and + 0.94 to + 6.5, respectively). The similar variation in bulk rock εNd(t) and zircon εHf(t) values and radiometric ages for the granites and gabbronorites indicate a genetic relationship between mafic and felsic magmas, either a crystal fractionation or silicate liquid immiscibility process; further work is needed to resolve petrogenetic details. The compositional characteristics of the bimodal Ghushchi complex are most consistent with magmatic activity in an extensional tectonic environment. This extension may have occurred during rifting of Cadomian fragments away from northern Gondwana during early phases of Neotethys opening.

Quantum effects of translational motions in solid para-hydrogen and ortho-deuterium: anharmonic extension of the Einstein model.

PubMed

Kühn, O; Manz, J; Schild, A

2010-04-07

An anharmonic extension of the Einstein model is developed in order to describe the effect of translational zero point motion on structural and thermodynamic properties of para-H(2) and ortho-D(2) crystals in the zero temperature limit. Accordingly, the molecules carry out large amplitude translational motions in their matrix cage, which are formed by the frozen environment of all other molecules. These translations lead from the molecular equilibrium positions via the harmonic to the anharmonic domain of the potential energy surface. The resulting translational distributions are roughly isotropic, and they have approximately Gaussian shapes, with rather broad full widths at half-maximum, FWHM(para-H(2)/ortho-D(2)) = 1.36/1.02 Å. The translational zero point energies induce expansions of the crystals, in nearly quantitative agreement with experimental results. Furthermore, they make significant contributions to the sublimation energies and zero pressure bulk moduli. These quantum effects decrease with heavier molecular masses. The corresponding isotope effects for ortho-D(2) compared to para-H(2) are confirmed by application of the model to Ar crystals. The results imply consequences for laser induced reaction dynamics of dopants with their host crystals.

Characterization of calcium isotopes in natural and synthetic barite

USGS Publications Warehouse

Griffith, E.M.; Schauble, E.A.; Bullen, T.D.; Paytan, A.

2008-01-01

The mineral barite (BaSO4) accommodates calcium in its crystal lattice, providing an archive of Ca-isotopes in the highly stable sulfate mineral. Holocene marine (pelagic) barite samples from the major ocean basins are isotopically indistinguishable from each other (??44/40Ca = -2.01 ?? 0.15???) but are different from hydrothermal and cold seep barite samples (??44/40Ca = -4.13 to -2.72???). Laboratory precipitated (synthetic) barite samples are more depleted in the heavy Ca-isotopes than pelagic marine barite and span a range of Ca-isotope compositions, ??44/40Ca = -3.42 to -2.40???. Temperature, saturation state, a Ba2 + / a SO42 -, and aCa2+/aBa2+ each influence the fractionation of Ca-isotopes in synthetic barite; however, the fractionation in marine barite samples is not strongly related to any measured environmental parameter. First-principles lattice dynamical modeling predicts that at equilibrium Ca-substituted barite will have much lower 44Ca/40Ca than calcite, by -9??? at 0 ??C and -8??? at 25 ??C. Based on this model, none of the measured barite samples appear to be in isotopic equilibrium with their parent solutions, although as predicted they do record lower ??44/40Ca values than seawater and calcite. Kinetic fractionation processes therefore most likely control the extent of isotopic fractionation exhibited in barite. Potential fractionation mechanisms include factors influencing Ca2+ substitution for Ba2+ in barite (e.g. ionic strength and trace element concentration of the solution, competing complexation reactions, precipitation or growth rate, temperature, pressure, and saturation state) as well as nucleation and crystal growth rates. These factors should be considered when investigating controls on isotopic fractionation of Ca2+ and other elements in inorganic and biogenic minerals. ?? 2008 Elsevier Ltd.

Zeolite Crystal Growth (ZCG) Flight on USML-2

NASA Technical Reports Server (NTRS)

Sacco, Albert, Jr.; Bac, Nurcan; Warzywoda, Juliusz; Guray, Ipek; Marceau, Michelle; Sacco, Teran L.; Whalen, Leah M.

1997-01-01

The extensive use of zeolites and their impact on the world's economy has resulted in many efforts to characterize their structure, and improve the knowledge base for nucleation and growth of these crystals. The zeolite crystal growth (ZCG) experiment on USML-2 aimed to enhance the understanding of nucleation and growth of zeolite crystals, while attempting to provide a means of controlling the defect concentration in microgravity. Zeolites A, X, Beta, and Silicalite were grown during the 16 day - USML-2 mission. The solutions where the nucleation event was controlled yielded larger and more uniform crystals of better morphology and purity than their terrestrial/control counterparts. The external surfaces of zeolite A, X, and Silicalite crystals grown in microgravity were smoother (lower surface roughness) than their terrestrial controls. Catalytic studies with zeolite Beta indicate that crystals grown in space exhibit a lower number of Lewis acid sites located in micropores. This suggests fewer structural defects for crystals grown in microgravity. Transmission electron micrographs (TEM) of zeolite Beta crystals also show that crystals grown in microgravity were free of line defects while terrestrial/controls had substantial defects.

Improved Success of Sparse Matrix Protein Crystallization Screening with Heterogeneous Nucleating Agents

PubMed Central

Thakur, Anil S.; Robin, Gautier; Guncar, Gregor; Saunders, Neil F. W.; Newman, Janet; Martin, Jennifer L.; Kobe, Bostjan

2007-01-01

Background Crystallization is a major bottleneck in the process of macromolecular structure determination by X-ray crystallography. Successful crystallization requires the formation of nuclei and their subsequent growth to crystals of suitable size. Crystal growth generally occurs spontaneously in a supersaturated solution as a result of homogenous nucleation. However, in a typical sparse matrix screening experiment, precipitant and protein concentration are not sampled extensively, and supersaturation conditions suitable for nucleation are often missed. Methodology/Principal Findings We tested the effect of nine potential heterogenous nucleating agents on crystallization of ten test proteins in a sparse matrix screen. Several nucleating agents induced crystal formation under conditions where no crystallization occurred in the absence of the nucleating agent. Four nucleating agents: dried seaweed; horse hair; cellulose and hydroxyapatite, had a considerable overall positive effect on crystallization success. This effect was further enhanced when these nucleating agents were used in combination with each other. Conclusions/Significance Our results suggest that the addition of heterogeneous nucleating agents increases the chances of crystal formation when using sparse matrix screens. PMID:17971854

The evolution of young silicic lavas at Medicine Lake Volcano, California: Implications for the origin of compositional gaps in calc-alkaline series lavas

USGS Publications Warehouse

Grove, T.L.; Donnelly-Nolan, J. M.

1986-01-01

At Medicine Lake Volcano, California, the compositional gap between andesite (57-62 wt.% SiO2) and rhyolite (73-74 wt.% SiO2) has been generated by fractional crystallization. Assimilation of silicic crust has also occurred along with fractionation. Two varieties of inclusions found in Holocene rhyolite flows, hornblende gabbros and aphyric andesites, provide information on the crystallization path followed by lavas parental to the rhyolite. The hornblende gabbros are magmatic cumulate residues and their mineral assemblages are preserved evidence of the phases that crystallized from an andesitic precursor lava to generate the rhyolite lavas. The andesitic inclusions represent samples of a parental andesite and record the early part of the differentiation history. Olivine, plagioclase and augite crystallization begins the differentiation history, followed by the disappearance of olivine and augite through reaction with the liquid to form orthopyroxene and amphibole. Further crystallization of the assemblage plagioclase, amphibole, orthopyroxene, magnetite, and apatite from a high-SiO2 andesite leads to rhyolite. This final crystallization process occurs on a cotectic that is nearly horizontal in temperature-composition space. Since a large amount of crystallization occurs over a limited temperature interval, a compositional gap develops between rhyolite and high SiO2 andesite. Liquidus surfaces with shallow slopes in temperature-composition space are characteristic of several late-stage crystallization assemblages in the andesite to rhyolite compositional range. Experimentally produced plagioclase+ amphibole+orthopyroxene+magnetite and plagioclase+ augite+low-Ca pyroxene+magnetite cotectics have liquidus slopes that are nearly flat. At other calc-alkaline volcanic centers crystallization processes involving large compositional changes over small temperature intervals may also be important in the development of bimodal volcanism (i.e. the existence of a composition gap). At Mt. Mazama and Mt. St. Helens, USA and Aso Caldera and Shikotsu, Japan the amphibole-bearing assemblage was important. At Krakatau, Indonesia and Katmai, USA, an augite+orthopyroxene-bearing assemblage was important. In addition to its role in the production of a compositional gap between intermediate and rhyolitic lavas, the crystallization process increases the H2O content of the residual liquid. This rapid increase in residual liquid volatile content which results from the precipitation of a large proportion of crystalline solids may be an important factor among several that lead to explosive silicic eruptions. ?? 1986 Springer-Verlag.

Contortionist bubbles in andesitic enclaves: implications for gas migration and phase segregation in crystal-rich magmas.

NASA Astrophysics Data System (ADS)

Oppenheimer, J. C.; Cashman, K. V.; Rust, A.; Dobson, K. J.; Bacon, C. R.; Dingwell, D. B.

2016-12-01

In order to constrain gas migration behaviors in crystal-rich magmas, we compare results of analogue experiments to frozen structures in andesitic enclaves. In the analogue experiments air was injected into mixtures of syrup and particles sandwiched between glass plates. We observed a significant increase in bubble deformation and coalescence when particle fractions increased beyond a critical value (the random loose packing). At high particle fractions, bubble growth re-organized (compacted) the particles adjacent to the bubble walls. This caused liquid segregation into patches within the particle suspension and into large void spaces near the outer edge of experiments. We compare these experiments to void morphologies in a 58 x 70 x 73 cm andesitic enclave from silicic-andesite lava flows of Mt Mazama, Oregon (Bacon, 1986). This enclave is zoned, with a vesicle-rich center and a glass-rich rim, suggesting gas-driven melt segregation from the center to the rim. We use both 2D (optical microscopy and SEM) and 3D (X-ray tomography) techniques to image crystal textures and bubble shapes. The center of the enclave bears scattered patches of groundmass in the main phenocryst framework. These patches are similar to those observed in experiments, and thus melt segregation in the enclave may have occurred both toward the rim and toward these patches. Bubble morphologies reveal two main types of bubbles. (1) Lobate and finger-like bubbles, similar to the deformed bubbles in experiments, are found exclusively in the groundmass patches. They are also often associated with compacted crystal structures at the bubble walls. (2) Diktytaxitic textures - angular bubbles flattened against phenocrysts - are abundant in the crystal networks. These voids are entirely connected in 3D and formed the gas-rich center of the enclave. They likely represent a gas migration regime where the expanding gas front cannot deform the crystal structure but instead invades the pore-space between crystals, pushing out residual melt (filter pressing). The switch between regimes appears to depend on crystal size and aspect ratio. The similar features between bubbles in the enclave and in experiments are encouraging, and suggest that crystal-induced bubble deformation, and gas-driven melt segregation, may be common in crystal-rich magmas.

Evolutionary Genomics of Defense Systems in Archaea and Bacteria*

PubMed Central

Koonin, Eugene V.; Makarova, Kira S.; Wolf, Yuri I.

2018-01-01

Evolution of bacteria and archaea involves an incessant arms race against an enormous diversity of genetic parasites. Accordingly, a substantial fraction of the genes in most bacteria and archaea are dedicated to antiparasite defense. The functions of these defense systems follow several distinct strategies, including innate immunity; adaptive immunity; and dormancy induction, or programmed cell death. Recent comparative genomic studies taking advantage of the expanding database of microbial genomes and metagenomes, combined with direct experiments, resulted in the discovery of several previously unknown defense systems, including innate immunity centered on Argonaute proteins, bacteriophage exclusion, and new types of CRISPR-Cas systems of adaptive immunity. Some general principles of function and evolution of defense systems are starting to crystallize, in particular, extensive gain and loss of defense genes during the evolution of prokaryotes; formation of genomic defense islands; evolutionary connections between mobile genetic elements and defense, whereby genes of mobile elements are repeatedly recruited for defense functions; the partially selfish and addictive behavior of the defense systems; and coupling between immunity and dormancy induction/programmed cell death. PMID:28657885

Structural modeling of G-protein coupled receptors: An overview on automatic web-servers.

PubMed

Busato, Mirko; Giorgetti, Alejandro

2016-08-01

Despite the significant efforts and discoveries during the last few years in G protein-coupled receptor (GPCR) expression and crystallization, the receptors with known structures to date are limited only to a small fraction of human GPCRs. The lack of experimental three-dimensional structures of the receptors represents a strong limitation that hampers a deep understanding of their function. Computational techniques are thus a valid alternative strategy to model three-dimensional structures. Indeed, recent advances in the field, together with extraordinary developments in crystallography, in particular due to its ability to capture GPCRs in different activation states, have led to encouraging results in the generation of accurate models. This, prompted the community of modelers to render their methods publicly available through dedicated databases and web-servers. Here, we present an extensive overview on these services, focusing on their advantages, drawbacks and their role in successful applications. Future challenges in the field of GPCR modeling, such as the predictions of long loop regions and the modeling of receptor activation states are presented as well. Copyright © 2016 Elsevier Ltd. All rights reserved.

Prediction of large gap flat Chern band in a two-dimensional metal-organic framework

NASA Astrophysics Data System (ADS)

Su, Ninghai; Jiang, Wei; Wang, Zhengfei; Liu, Feng

2018-01-01

Systems with a flat Chern band have been extensively studied for their potential to realize high-temperature fractional quantum Hall states. To experimentally observe the quantum transport properties, a sizable topological gap is highly necessary. Here, taking advantage of the high tunability of two-dimensional (2D) metal-organic frameworks (MOFs), whose crystal structures can be easily tuned using different metal atoms and molecular ligands, we propose a design of a 2D MOF [Tl2(C6H4)3, Tl2Ph3] showing nontrivial topological states with an extremely large gap in both the nearly flat Chern band and the Dirac bands. By coordinating π-conjugated thallium ions and benzene rings, crystalline Tl2Ph3 can be formed with Tl and Ph constructing honeycomb and kagome lattices, respectively. The px,y orbitals of Tl on the honeycomb lattice form ideal pxy four-bands, through which a flat Chern band with a spin-orbit coupling (SOC) gap around 140 meV evolves below the Fermi level. This is the largest SOC gap among all the theoretically proposed organic topological insulators so far.

Scanning and Transmission Electron Microscopy of High Temperature Materials

NASA Technical Reports Server (NTRS)

1994-01-01

Software and hardware updates to further extend the capability of the electron microscope were carried out. A range of materials such as intermetallics, metal-matrix composites, ceramic-matrix composites, ceramics and intermetallic compounds, based on refractory elements were examined under this research. Crystal structure, size, shape and volume fraction distribution of various phases which constitute the microstructures were examined. Deformed materials were studied to understand the effect of interfacial microstructure on the deformation and fracture behavior of these materials. Specimens tested for a range of mechanical property requirements, such as stress rupture, creep, low cycle fatigue, high cycle fatigue, thermomechanical fatigue, etc. were examined. Microstructural and microchemical stability of these materials exposed to simulated operating environments were investigated. The EOIM Shuttle post-flight samples were also examined to understand the influence of low gravity processing on microstructure. In addition, fractographic analyses of Nb-Zr-W, titanium aluminide, molybdenum silicide and silicon carbide samples were carried out. Extensive characterization of sapphire fibers in the fiber-reinforced composites made by powder cloth processing was made. Finally, pressure infiltration casting of metal-matrix composites was carried out.

Re-187-Os-187, Pt-190-Os-186 Isotopic and Highly Siderophile Element Systematics of Group IVA Irons

NASA Technical Reports Server (NTRS)

Walker, R. J.; McCoy, T. J.; Schulte, R. F.; McDonough, W. F.; Ash, R. D.

2005-01-01

We have recently completed Re-187-Os-187 and Pt-190-Os-186 isotopic and elemental studies of the two largest magmatic iron meteorite groups, IIAB and IIIAB [1]. These studies revealed closed-system behavior of both isotopic systems, but complex trace element behavior for Re, Pt and Os in group IIIAB. Here we examine isotopic and trace elemental systematics of group IVA irons. The IVA irons are not as extensively fractionated as IIAB and IIIAB and their apparently less complex crystallization history may make for more robust interpretation of the relative partitioning behavior of Re, Pt and Os, as well as the other highly siderophile elements (HSE) measured here; Pd, Ru and Ir [e.g. 2]. An additional goal of our continuing research plan for iron meteorites is to assess the possibility of relating certain ungrouped irons with major groups via trace element modeling. Here, the isotopic and trace element systematics of the ungrouped irons Nedagolla and EET 83230 are compared with the IVA irons.

Evidence of varying magma chambers and magmatic evolutionary histories for the Table Mountain Formation in the Carson-Iceberg Wilderness region, Sonora Pass, California

NASA Astrophysics Data System (ADS)

Asami, R.; Putirka, K. D.; Pluhar, C. J.; Farner, M. J.; Torrez, G.; Shrum, B. L.; Jones, S.

2012-12-01

The Sonora Pass- Dardanelles region in the Carson- Iceberg Wilderness area is located in the central Sierra Nevada and home to the type section for latites (Slemmons, 1953), a volcanic rock that contains high potassium, clinopyroxene, and plagioclase phenocysts. Latite lavas and tuffs exposed in the Sonora Pass region originated from the sources in the eastern Sierra Nevada (Noble et al., 1974) where lavas flowed toward California's Great Valley, and were emplaced in stream valleys along the way, which are now inverted to form "table mountains", ergo the name "Table Mountain Latite" (TML) (Slemmons, 1966). Similarly high-K volcanic rocks of the same age are exposed at Grouse Meadows, which is just north of the Walker Lane Caldera east of Sonora Pass, and at the type section, between Red Peak and Bald Peak west of Sonora Pass. Latites lavas and tuffs in all three regions were analyzed for major oxides and trace elements with X-ray fluorescence spectrometry at California State University, Fresno. Analysis of three locations of (TML) at the type section show that they (Ransome, 1898), may have a different magmatic evolutionary history compared to other latites, exposed at Sonora Pass and Grouse Meadows, as the latter two show similar major oxide and trace element compositions. Most compelling is the contrast in the behavior of Al2O3 and CaO at the type section. Variation diagrams show that at the type section Al2O3 and CaO enrichment decreases with increasing amounts of MgO as fractional crystallization occurs. Conversely, at Sonora Peak and Grouse Meadows, CaO and Al2O3 concentrations mostly increase as MgO decreases with fractional crystallization. This contrasts shows that plagioclase was a major fractioning phase at the type section, but not at the other two localities. This suggests that the lava flows at the type section were erupted from a distinct set of magma chambers and vents that underwent a very distinct magmatic evolutionary history, perhaps involving fractionation at shallower depths compared to the Sonora Pass and Grouse Meadows flows, which appear to evolve by clinopyroxene fractionation. These contrasts in the pressures of crystal fractionation may be the result of contrasts in crustal structure or tectonic setting, an issue currently being investigated.

(NZ)CH...O contacts assist crystallization of a ParB-like nuclease.

PubMed

Shaw, Neil; Cheng, Chongyun; Tempel, Wolfram; Chang, Jessie; Ng, Joseph; Wang, Xin-Yu; Perrett, Sarah; Rose, John; Rao, Zihe; Wang, Bi-Cheng; Liu, Zhi-Jie

2007-07-07

The major bottleneck for determination of 3 D structures of proteins using X-rays is the production of diffraction quality crystals. Often proteins are subjected to chemical modification to improve the chances of crystallization Here, we report the successful crystallization of a nuclease employing a reductive methylation protocol. The key to crystallization was the successful introduction of 44 new cohesive (NZ) CH...O contacts (3.2-3.7 A) by the addition of 2 methyl groups to the side chain amine nitrogen (NZ) of 9 lysine residues of the nuclease. The new contacts dramatically altered the crystallization properties of the protein, resulting in crystals that diffracted to 1.2 A resolution. Analytical ultracentrifugation analysis and thermodynamics results revealed a more compact protein structure with better solvent exclusion of buried Trp residues in the folded state of the methylated protein, assisting crystallization. In this study, introduction of novel cohesive (NZ)CH...O contacts by reductive methylation resulted in the crystallization of a protein that had previously resisted crystallization in spite of extensive purification and crystallization space screening. Introduction of (NZ)CH...O contacts could provide a solution to crystallization problems for a broad range of protein targets.

On the singular perturbations for fractional differential equation.

PubMed

Atangana, Abdon

2014-01-01

The goal of this paper is to examine the possible extension of the singular perturbation differential equation to the concept of fractional order derivative. To achieve this, we presented a review of the concept of fractional calculus. We make use of the Laplace transform operator to derive exact solution of singular perturbation fractional linear differential equations. We make use of the methodology of three analytical methods to present exact and approximate solution of the singular perturbation fractional, nonlinear, nonhomogeneous differential equation. These methods are including the regular perturbation method, the new development of the variational iteration method, and the homotopy decomposition method.

Confined crystallization, crystalline phase deformation and their effects on the properties of crystalline polymers

NASA Astrophysics Data System (ADS)

Wang, Haopeng

With the recent advances in processing and catalyst technology, novel morphologies have been created in crystalline polymers and they are expected to substantially impact the properties. To reveal the structure-property relationships of some of these novel polymeric systems becomes the primary focus of this work. In the first part, using an innovative layer-multiplying coextrusion process to obtain assemblies with thousands of polymer nanolayers, dominating "in-plane" lamellar crystals were created when the confined poly(ethylene oxide) (PEO) layers were made progressively thinner. When the thickness was confined to 25 nanometers, the PEO crystallized as single, high-aspect-ratio lamellae that resembled single crystals. This crystallization habit imparted more than two orders of magnitude reduction in the gas permeability. The dramatic decrease in gas permeability was attributed to the reduced diffusion coefficient, because of the increase in gas diffusion path length through the in-plane lamellae. The temperature dependence of lamellar orientation and the crystallization kinetics in the confined nanolayers were also investigated. The novel olefinic block copolymer (OBC) studied in the second part consisted of long crystallizable sequences with low comonomer content alternating with rubbery amorphous blocks with high comonomer content. The crystallizable blocks formed lamellae that organized into space-filling spherulites even when the fraction of crystallizable block was so low that the crystallinity was only 7%. These unusual spherulites were highly elastic and recovered from strains as high as 300%. These "elastic spherulites" imparted higher strain recovery and temperature resistance than the conventional random copolymers that depend on isolated, fringed micellar-like crystals to provide the junctions for the elastomeric network. In the third part, positron annihilation lifetime spectroscopy (PALS) was used to obtain the temperature dependence of the free volume hole size in propylene/ethylene copolymers over a range in comonomer content. Above the glass transition temperature (Tg), the reduced free volume hole size and the densification of the amorphous phase were attributed to constraint imposed on rubbery amorphous chain segments by attached chain segments in crystals. However constant free volume fraction was found at Tg, across the crystallinity range of the copolymers, in agreement with the iso-free volume concept of glass transition.

CrystalMoM: a tool for modeling the evolution of Crystals Size Distributions in magmas with the Method of Moments

NASA Astrophysics Data System (ADS)

Colucci, Simone; de'Michieli Vitturi, Mattia; Landi, Patrizia

2016-04-01

It is well known that nucleation and growth of crystals play a fundamental role in controlling magma ascent dynamics and eruptive behavior. Size- and shape-distribution of crystal populations can affect mixture viscosity, causing, potentially, transitions between effusive and explosive eruptions. Furthermore, volcanic samples are usually characterized in terms of Crystal Size Distribution (CSD), which provide a valuable insight into the physical processes that led to the observed distributions. For example, a large average size can be representative of a slow magma ascent, and a bimodal CSD may indicate two events of nucleation, determined by two degassing events within the conduit. The Method of Moments (MoM), well established in the field of chemical engineering, represents a mesoscopic modeling approach that rigorously tracks the polydispersity by considering the evolution in time and space of integral parameters characterizing the distribution, the moments, by solving their transport differential-integral equations. One important advantage of this approach is that the moments of the distribution correspond to quantities that have meaningful physical interpretations and are directly measurable in natural eruptive products, as well as in experimental samples. For example, when the CSD is defined by the number of particles of size D per unit volume of the magmatic mixture, the zeroth moment gives the total number of crystals, the third moment gives the crystal volume fraction in the magmatic mixture and ratios between successive moments provide different ways to evaluate average crystal length. Tracking these quantities, instead of volume fraction only, will allow using, for example, more accurate viscosity models in numerical code for magma ascent. Here we adopted, for the first time, a quadrature based method of moments to track the temporal evolution of CSD in a magmatic mixture and we verified and calibrated the model again experimental data. We also show how the equations and the tool developed can be integrated in a magma ascent numerical model, with application to eruptive events occurred at Stromboli volcano (Italy).

Self-organisation of semi-flexible rod-like particles

NASA Astrophysics Data System (ADS)

de Braaf, Bart; Oshima Menegon, Mariana; Paquay, Stefan; van der Schoot, Paul

2017-12-01

We report on a comprehensive computer simulation study of the liquid-crystal phase behaviour of purely repulsive, semi-flexible rod-like particles. For the four aspect ratios we consider, the particles form five distinct phases depending on their packing fraction and bending flexibility: the isotropic, nematic, smectic A, smectic B, and crystal phase. Upon increasing the particle bending flexibility, the various phase transitions shift to larger packing fractions. Increasing the aspect ratio achieves the opposite effect. We find two different ways in which the layer thickness of the particles in the smectic A phase may respond to an increase in concentration. The layer thickness may either decrease or increase depending on the aspect ratio and flexibility. For the smectic B and the crystalline phases, increasing the concentration always decreases the layer thickness. Finally, we find that the layer spacing jumps to a larger value on transitioning from the smectic A phase to the smectic B phase.

Purification, characterization, and crystallization of monoamine oxidase from Escherichia coli K-12.

PubMed

Roh, J H; Suzuki, H; Azakami, H; Yamashita, M; Murooka, Y; Kumagai, H

1994-09-01

The gene for monoamine oxidase (MAO) was cloned from an Escherichia coli genomic library and MAO was overproduced in the periplasmic space. The enzyme was purified to homogeneity by preparation of a periplasmic fraction, followed by ammonium sulfate fractionation and DEAE-cellulose column chromatography. Crystals were obtained by the hanging drop method using sodium citrate as a precipitant. The enzyme was found to be a dimer of identical subunits with a molecular weight of 80,000, and showed the highest activity at pH 7.5 and 45 degrees C. The enzyme was inhibited by a MAO specific inhibitor, hydroxylamine, hydrazine, phenelzine, isoniazid, and tranycpromine. The enzyme oxidized tyramine, phenethylamine, and tryptamine at higher rates, but not oxidized diamine and polyamines such as putrescine and spermine. The antibody against E. coli MAO cross-reacted with purified MAO A from Klebsiella aerogenes.

Phase and vacancy behaviour of hard "slanted" cubes

NASA Astrophysics Data System (ADS)

van Damme, R.; van der Meer, B.; van den Broeke, J. J.; Smallenburg, F.; Filion, L.

2017-09-01

We use computer simulations to study the phase behaviour for hard, right rhombic prisms as a function of the angle of their rhombic face (the "slant" angle). More specifically, using a combination of event-driven molecular dynamics simulations, Monte Carlo simulations, and free-energy calculations, we determine and characterize the equilibrium phases formed by these particles for various slant angles and densities. Surprisingly, we find that the equilibrium crystal structure for a large range of slant angles and densities is the simple cubic crystal—despite the fact that the particles do not have cubic symmetry. Moreover, we find that the equilibrium vacancy concentration in this simple cubic phase is extremely high and depends only on the packing fraction and not the particle shape. At higher densities, a rhombic crystal appears as the equilibrium phase. We summarize the phase behaviour of this system by drawing a phase diagram in the slant angle-packing fraction plane.

Chain Confinement in Electrospun Nanocomposites: using Thermal Analysis to Investigate Polymer-Filler Interactions

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

Q Ma; B Mao; P Cebe

2011-12-31

We investigate the interaction of the polymer matrix and filler in electrospun nanofibers using advanced thermal analysis methods. In particular, we study the ability of silicon dioxide nanoparticles to affect the phase structure of poly(ethylene terephthalate), PET. SiO{sub 2} nanoparticles (either unmodified or modified with silane) ranging from 0 to 2.0 wt% in PET were electrospun from hexafluoro-2-propanol solutions. The morphologies of both the electrospun (ES) nanofibers and the SiO{sub 2} powders were observed by scanning and transmission electron microscopy, while the amorphous or crystalline nature of the fibers was determined by real-time wide-angle X-ray scattering. The fractions of themore » crystal, mobile amorphous, and rigid amorphous phases of the non-woven, nanofibrous composite mats were quantified by using heat capacity measurements. The amount of the immobilized polymer layer, the rigid amorphous fraction, was obtained from the specific reversing heat capacity for both as-spun amorphous fibers and isothermally crystallized fibers. Existence of the rigid amorphous phase in the absence of crystallinity was verified in nanocomposite fibers, and two origins for confinement of the rigid amorphous fraction are proposed. Thermal analysis of electrospun fibers, including quasi-isothermal methods, provides new insights to quantitatively characterize the polymer matrix phase structure and thermal transitions, such as devitrification of the rigid amorphous fraction.« less

Comparative analysis of thermal behavior, isothermal crystallization kinetics and polymorphism of palm oil fractions.

PubMed

Zhang, Xia; Li, Lin; Xie, He; Liang, Zhili; Su, Jianyu; Liu, Guoqin; Li, Bing

2013-01-15

Thermal behavior of palm stearin (PS) and palm olein (PO) was explored by monitoring peak temperature transitions by differential scanning calorimetry (DSC). The fatty acid composition (FAC), isothermal crystallization kinetics studied by pulsed Nuclear Magnetic Resonance (pNMR) and isothermal microstructure were also compared. The results indicated that the fatty acid composition had an important influence on the crystallization process. PS and PO both exhibited more multiple endotherms than exotherms which showed irregular peak shapes. An increasing in cooling rate, generally, was associated with an increase in peak size. Application of the Avaimi equation to isothermal crystallization of PS and PO revealed different nucleation and growth mechanisms based on the Avrami exponents. PS quickly reached the end of crystallization because of more saturated triacylglycerol (TAG). The Avrami index of PS were the same as PO under the same isothermal condition at lower temperatrue, indicating that the crystallization mechanism of the two samples based on super-cooling state were the same. According to the polarized light microscope (PLM) images, crystal morphology of PS and PO was different. With the temperature increased, the structure of crystal network of both PS and PO gradually loosened.

Evolution of Micro-Pores in a Single-Crystal Nickel-Based Superalloy During Solution Heat Treatment

NASA Astrophysics Data System (ADS)

Li, Xiangwei; Wang, Li; Dong, Jiasheng; Lou, Langhong; Zhang, Jian

2017-06-01

Evolution of micro-pores in a third-generation single-crystal nickel-based superalloy during solution heat treatment at 1603 K (1330 °C) was investigated by X-ray computed tomography. 3D information including morphology, size, number, and volume fraction of micro-pores formed during solidification (S-pores) and solution (H-pores) was analyzed. The growth behaviors of both S-pores and H-pores can be related to the vacancy formation and diffusion during heat treatment.

Optically stimulated luminescence dating of sediments

NASA Astrophysics Data System (ADS)

Troja, S. O.; Amore, C.; Barbagallo, G.; Burrafato, G.; Forzese, R.; Geremia, F.; Gueli, A. M.; Marzo, F.; Pirnaci, D.; Russo, M.; Turrisi, E.

2000-04-01

Optically stimulated luminescence (OSL) dating methodology was applied on the coarse grain fraction (100÷500 μm thick) of quartz crystals (green light stimulated luminescence, GLSL) and feldspar crystals (infrared stimulated luminescence, IRSL) taken from sections at different depths of cores bored in various coastal lagoons (Longarini, Cuba, Bruno) in the south-east coast of Sicily. The results obtained give a sequence of congruent relative ages and maximum absolute ages compatible with the sedimentary structure, thus confirming the excellent potential of the methodology.

Origins of cryptic variation in the Ediacaran-Fortunian rhyolitic ignimbrites of the Saldanha Bay Volcanic Complex, Western Cape, South Africa

NASA Astrophysics Data System (ADS)

Clemens, J. D.; Stevens, G.; Frei, D.; Joseph, C. S. A.

2017-12-01

The Saldanha eruption centre, on the West Coast of South Africa, consists of 542 Ma, intracaldera, S-type, rhyolite ignimbrites divided into the basal Saldanha Ignimbrite and the partly overlying Jacob's Bay Ignimbrite. Depleted-mantle Nd model ages suggest magma sources younger than the Early Mesoproterozoic, and located within the Neoproterozoic Malmesbury Group and Swartland complex metasedimentary and metavolcanic rocks that form the regional basement. The Sr isotope systematics suggest that the dominant source rocks were metavolcaniclastic rocks and metagreywackes, and that the magmas formed from separate batches extracted from the same heterogeneous source. No apparent magma mixing trends relate the Saldanha to the Jacob's Bay Ignimbrites, or either of these to the magmas that formed the Plankiesbaai or Tsaarsbank Ignimbrites in the neighbouring Postberg eruption centre. The magmas were extracted from their source rocks carrying small but significant proportions of peritectic and restitic accessory minerals. Variations in the content of this entrained crystal cargo were responsible for most of the chemical variations in the magmas. Although we cannot construct a cogent crystal fractionation model to relate these groups of magmas, at least some crystal fractionation occurred, as an overlay on the primary signal due to peritectic assemblage entrainment (PAE). Thus, the causes of the cryptic chemical variation among the ignimbrite magmas of the Saldanha centre are variable, but dominated by the compositions of the parent melts and PAE. The preservation of clear, source-inherited chemical signatures, in individual samples, calls into question the common interpretation of silicic calderas as having been formed in large magma reservoirs, with magma compositions shaped by magma mingling, mixing, and fractional crystallization. The Saldanha rocks suggest a more intimate connection between source and erupted magma, and perhaps indicate that silicic magmas are too viscous to be significantly modified by magma-chamber processes.

In situ major and trace element analysis of amphiboles in quartz monzodiorite porphyry from the Tonglvshan Cu-Fe (Au) deposit, Hubei Province, China: insights into magma evolution and related mineralization

NASA Astrophysics Data System (ADS)

Duan, Deng-Fei; Jiang, Shao-Yong

2017-05-01

The Tonglvshan deposit is the largest Cu-Fe (Au) skarn deposit in the Edong district, which is located in the westernmost part of the Middle and Lower Yangtze River metallogenic belt, China. In this study, we performed a detailed in situ analysis of major and trace elements in amphiboles from the ore-related Tonglvshan quartz monzodiorite porphyry using electron microprobe (EMPA) analysis and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Two distinct populations of amphiboles, which can be distinguished by their aluminum content, are found in the quartz monzodiorite porphyry. The low-aluminum (Low-Al) amphiboles are subhedral or anhedral and formed at 46.3-73.5 MPa and 713-763 °C. In contrast, the high-aluminum (High-Al) amphiboles are euhedral and formed at 88-165 MPa and 778-854 °C. Some euhedral amphiboles are partially or completely replaced by Low-Al amphibole. The compositions of parental melts in equilibrium with the High-Al amphibole ( Melt 1) and Low-Al amphibole ( Melt 2) were computed by applying solid/liquid partition coefficients. This modeling shows that magma in equilibrium with High-Al amphibole ( Melt 1) underwent 40% fractional crystallization of amphibole, plagioclase and apatite at a depth of 5 km to evolve to magma in equilibrium with Low-Al amphibole ( Melt 2). Copper enrichment occurred in the magma after undergoing fractional crystallization. The magma had a high oxygen fugacity, increasing from NNO + 1 ( Melt 1) through NNO + 2 to HM ( Melt 2), which could have prevented the loss of Cu (and possibly Au) to sulfide minerals during crystallization. Finally, the evolved magma intruded to shallower depths, where it presumably exsolved aqueous ore-forming fluids. Therefore, the large Cu-Fe-Au reserves of the Tonglvshan deposit can likely be attributed to a combination of controlling factors, including high oxygen fugacity, fractional crystallization, fluid exsolution, and a shallow emplacement depth.

Classification of Arctic, Mid-Latitude and Tropical Clouds in the Mixed-Phase Temperature Regime

NASA Astrophysics Data System (ADS)

Costa, Anja; Afchine, Armin; Luebke, Anna; Meyer, Jessica; Dorsey, James R.; Gallagher, Martin W.; Ehrlich, André; Wendisch, Manfred; Krämer, Martina

2016-04-01

The degree of glaciation and the sizes and habits of ice particles formed in mixed-phase clouds remain not fully understood. However, these properties define the mixed clouds' radiative impact on the Earth's climate and thus a correct representation of this cloud type in global climate models is of importance for an improved certainty of climate predictions. This study focuses on the occurrence and characteristics of two types of clouds in the mixed-phase temperature regime (238-275K): coexistence clouds (Coex), in which both liquid drops and ice crystals exist, and fully glaciated clouds that develop in the Wegener-Bergeron-Findeisen regime (WBF clouds). We present an extensive dataset obtained by the Cloud and Aerosol Particle Spectrometer NIXE-CAPS, covering Arctic, mid-latitude and tropical regions. In total, we spent 45.2 hours within clouds in the mixed-phase temperature regime during five field campaigns (Arctic: VERDI, 2012 and RACEPAC, 2014 - Northern Canada; mid-latitude: COALESC, 2011 - UK and ML-Cirrus, 2014 - central Europe; tropics: ACRIDICON, 2014 - Brazil). We show that WBF and Coex clouds can be identified via cloud particle size distributions. The classified datasets are used to analyse temperature dependences of both cloud types as well as range and frequencies of cloud particle concentrations and sizes. One result is that Coex clouds containing supercooled liquid drops are found down to temperatures of -40 deg C only in tropical mixed clouds, while in the Arctic and mid-latitudes no liquid drops are observed below about -20 deg C. In addition, we show that the cloud particles' aspherical fractions - derived from polarization signatures of particles with diameters between 20 and 50 micrometers - differ significantly between WBF and Coex clouds. In Coex clouds, the aspherical fraction of cloud particles is generally very low, but increases with decreasing temperature. In WBF clouds, where all cloud particles are ice, about 20-40% of the cloud particles are nevertheless classified as spherical for all temperatures, possibly indicating columnar ice crystals (see Järvinen et al, submitted to JAS 2016).

An Apollo 15 Mare Basalt Fragment and Lunar Mare Provinces

NASA Technical Reports Server (NTRS)

Ryder, Graham; Burling, Trina Cox

1996-01-01

Lunar sample 15474,4 is a tiny fragment of olivine-augite vitrophyre that is a mare basalt. Although petroraphically distinct from all other Apollo 15 samples, it has been ignored since its first brief description. Our new petrographic and mineral chemical data show that the olivines and pyroxenes are distinct from those in other basalts. The basalt cooled and solidified extremely rapidly; some of the olivine might be cumulate or crystallized prior to extrusion. Bulk-chemical data show that the sample is probably similar to an evolved Apollo 15 olivine-normative basalt in major elements but is distinct in its rare earth element pattern. Its chemical composition and petrography both show that 15474,4 cannot be derived from other Apollo 15 mare basalts by shallow-level crystal fractionation. It represents a distinct extrusion of magma. Nonetheless, the chemical features that 15474,4 has in common with other Apollo 15 mare basalts, including the high FeO/Sc, the general similarity of the rare earth element pattern, and the common (and chondritic) TiO2/Sm ratio, emphasize the concept of a geochemical province at the Apollo 15 site that is distinct from basalts and provinces elsewhere. In making a consistent picture for the derivation of all of the Apollo 15 basalts, both the commonalities and the differences among the basalts must be explained. The Apollo 15 commonalities and differences suggest that the sources must have consisted of major silicate phases with the same composition but with varied amounts of a magma trapped from a contemporary magma ocean. They probably had a high olivine/pyroxene ratio and underwent small and reasonably consistent degrees of partial melting to produce the basalts. These inferences may be inconsistent with models that suggest greatly different depths of melting among basalts, primitive sources for the green glasses, or extensive olivine fractionation during ascent. An integrated approach to lunar mare provinces, of which the Apollo 15 mare basalts constitute only one, offers advances in our understanding of the physical and chemical processes of source formation and mare production but has so far not been utilized.

Effect of Melting Point on the Physical Properties of Anhydrous Milk Fat

NASA Astrophysics Data System (ADS)

Wang, Yunna; Li, Yang; Han, Jie; Li, Yan; Zhang, Liebing

2017-12-01

The effect of melting point on the physical properties of anhydrous milk fat were investigated. The results showed that high melting fractions (HMF) (S30,S35) were enriched in long-chain fatty acids, whereas low melting fractions (LMF)(S5,S10,S15) were enriched in short-chain and unsaturated fatty acids. From S5 to S35, enthalpy value was gradually increased on both crystallization and melting condition, so as SFC on different temperature. The mixture and chemical interesterification allowed obtaining fats with various degrees of plasticity, increasing the possibilities for the commercial use of different fraction of AMF.

Barium isotope fractionation during the experimental transformation of aragonite to witherite and of gypsum to barite, and the effect of ion (de)solvation.

PubMed

Böttcher, Michael E; Neubert, Nadja; von Allmen, Katja; Samankassou, Elias; Nägler, Thomas F

2018-06-01

In this study, we present the experimental results for stable barium (Ba) isotope fractionation ( 137 Ba/ 134 Ba) during the transformation of aragonite (CaCO 3 ) and gypsum (CaSO 4 ·2H 2 O) in Ba-bearing aqueous solution to witherite (BaCO 3 ) and barite (BaSO 4 ), respectively. The process was studied at three temperatures between 4 and 60 °C. In all cases, the transformation leads to a relative enrichment of the lighter 134 Ba isotope in the solid compared to the aqueous solution, with 137/134 Ba enrichment factors between -0.11 and -0.17 ‰ for BaCO 3 , and -0.21 and -0.26 ‰ for BaSO 4 . The corresponding mass-dependent 138/134 Ba enrichment factors are -0.15 to -0.23 ‰ for BaCO 3 , and -0.28 to -0.35 ‰ for BaSO 4 . The magnitude of isotope fractionation is within the range of recent reports for witherite and barite formation, as well as trace Ba incorporation into orthorhombic aragonite, and no substantial impact of temperature can be found between 4 and 80 °C. In previous studies, ion (de)solvation has been suggested to impact both the crystallization process of Ba-bearing solids and associated Ba isotope fractionation. Precipitation experiments of BaSO 4 and BaCO 3 using an methanol-containing aqueous solution indicate only a minor effect of ion and crystal surface (de)solvation on the overall Ba isotope fractionation process.

Aerosolization properties, surface composition and physical state of spray-dried protein powders.

PubMed

Bosquillon, Cynthia; Rouxhet, Paul G; Ahimou, François; Simon, Denis; Culot, Christine; Préat, Véronique; Vanbever, Rita

2004-10-19

Powder aerosols made of albumin, dipalmitoylphosphatidylcholine (DPPC) and a protein stabilizer (lactose, trehalose or mannitol) were prepared by spray-drying and analyzed for aerodynamic behavior, surface composition and physical state. The powders exited a Spinhaler inhaler as particle aggregates, the size of which depending on composition, spray-drying parameters and airflow rate. However, due to low bulk powder tap density (<0.15 g/cm3), the aerodynamic size of a large fraction of aggregates remained respirable (<5 microm). Fine particle fractions ranged between 21% and 41% in an Andersen cascade impactor operated at 28.3 l/min, with mannitol and lactose providing the most cohesive and free-flowing powders, respectively. Particle surface analysis by X-ray photoelectron spectroscopy (XPS) revealed a surface enrichment with DPPC relative to albumin for powders prepared under certain spray-drying conditions. DPPC self-organized in a gel phase in the particle and no sugar or mannitol crystals were detected by X-ray diffraction. Water sorption isotherms showed that albumin protected lactose from moisture-induced crystallization. In conclusion, a proper combination of composition and spray-drying parameters allowed to obtain dry powders with elevated fine particle fractions (FPFs) and a physical environment favorable to protein stability.

Aluminum enrichment in silicate melts by fractional crystallization: some mineralogic and petrographic constraints.

USGS Publications Warehouse

Zen, E.

1986-01-01

The degree of Al saturation of an igneous rock may be given by its aluminium saturation index (ASI), defined as the molar ratio Al2O3/(CaO+K2O+Na2O). One suggested origin for mildly peraluminous granites (ASI 1-1.1) is fractional crystallization of subaluminous magmas (ASI 1. For hornblende to effectively cause a melt to evolve into a peraluminous composition, it must be able to coexist with peraluminous magmas; e.g. at = or <5 kbar hornblende can coexist with strongly peraluminous melts (ASI approx 1.5). Potentials and problems of using coarse-grained granitic rocks to prove courses of magmatic evolution are illustrated by a suite of samples from the Grayling Lake pluton, SW Montana. Such rocks generally contain a large cumulate component and should not be used as a primary test for the occurrence or efficacy of a fractionation process that might lead to peraluminous melts. The process is unlikely to give rise to peraluminous plutons of batholithic dimensions. A differential equation is presented which allows the direct use of mineral chemistry and modal abundance to predict the path of incremental evolution of a given magma.-R.A.H.

Characterization of molecular associations involving L-ornithine and α-ketoglutaric acid: crystal structure of L-ornithinium α-ketoglutarate.

PubMed

Allouchi, H; Céolin, R; Berthon, L; Tombret, F; Rietveld, I B

2014-07-01

The crystal structure of L-ornithinium α-ketoglutarate (C5H13N2O2, C5H5O5) has been solved by direct methods using single crystal X-ray diffraction data. It crystallizes in the monoclinic system, space group P21, unit cell parameters a=15.4326(3), b=5.2015(1), c=16.2067(3) Å and β=91.986(1)°, containing two independent pairs of molecular ions in the asymmetric unit. An extensive hydrogen-bond network and electrostatic charges due to proton transfer provide an important part of the cohesive energy of the crystal. The conformational versatility of L-ornithine and α-ketoglutaric acid is illustrated by the present results and crystal structures available from the Cambridge Structural Database. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

Effects of Microstructural Parameters on Creep of Nickel-Base Superalloy Single Crystals

NASA Technical Reports Server (NTRS)

MacKay, Rebecca A.; Gabb, Timothy P.; Nathal, Michael V.

2013-01-01

Microstructure-sensitive creep models have been developed for Ni-base superalloy single crystals. Creep rupture testing was conducted on fourteen single crystal alloys at two applied stress levels at each of two temperatures, 982 and 1093 C. The variation in creep lives among the different alloys could be explained with regression models containing relatively few microstructural parameters. At 982 C, gamma-gamma prime lattice mismatch, gamma prime volume fraction, and initial gamma prime size were statistically significant in explaining the creep rupture lives. At 1093 C, only lattice mismatch and gamma prime volume fraction were significant. These models could explain from 84 to 94 percent of the variation in creep lives, depending on test condition. Longer creep lives were associated with alloys having more negative lattice mismatch, lower gamma prime volume fractions, and finer gamma prime sizes. The gamma-gamma prime lattice mismatch exhibited the strongest influence of all the microstructural parameters at both temperatures. Although a majority of the alloys in this study were stable with respect to topologically close packed (TCP) phases, it appeared that up to approximately 2 vol% TCP phase did not affect the 1093 C creep lives under applied stresses that produced lives of approximately 200 to 300 h. In contrast, TCP phase contents of approximately 2 vol% were detrimental at lower applied stresses where creep lives were longer. A regression model was also developed for the as-heat treated initial gamma prime size; this model showed that gamma prime solvus temperature, gamma-gamma prime lattice mismatch, and bulk Re content were all statistically significant.

Chemical heterogeneities in the interior of terrestrial bodies

NASA Astrophysics Data System (ADS)

Plesa, Ana-Catalina; Maurice, Maxime; Tosi, Nicola; Breuer, Doris

2016-04-01

Mantle chemical heterogeneities that can strongly influence the interior dynamics have been inferred for all terrestrial bodies of the Solar System and range from local to global scale. Seismic data for the Earth, differences in surface mineral compositions observed in data sets from space missions, and isotopic variations identified in laboratory analyses of meteorites or samples indicate chemically heterogeneous systems. One way to generate large scale geochemical heterogeneities is through the fractional crystallization of a liquid magma ocean. The large amount of energy available in the early stages of planetary evolution can cause melting of a significant part or perhaps even the entire mantle of a terrestrial body resulting in a liquid magma ocean. Assuming fractional crystallization, magma ocean solidification proceeds from the core-mantle boundary to the surface where dense cumulates tend to form due to iron enrichment in the evolving liquid. This process leads to a gravitationally unstable mantle, which is prone to overturn. Following cumulate overturn, a stable stratification may be reached that prevents efficient material transport. As a consequence, mantle reservoirs may be kept separate, possibly for the entire thermo-chemical evolution of a terrestrial body. Scenarios assuming fractional crystallization of a liquid magma ocean have been suggested to explain lavas with distinct composition on Mercury's surface [1], the generation of the Moon's mare basalts by sampling a reservoir consisting of overturned ilmenite-bearing cumulates [2], and the preservation of Mars' geochemical reservoirs as inferred by isotopic analysis of the SNC meteorites [3]. However, recent studies have shown that the style of the overturn as well as the subsequent density stratification are of extreme importance for the subsequent thermo-chemical evolution of a planetary body and may have a major impact on the later surface tectonics and volcanic history. The rapid formation of a stagnant lid that traps the uppermost dense cumulates close to the surface and prevents them from sinking into the mantle or the difficulty to initiate thermal convection because of the stable compositional gradient established after the overturn are difficult to reconcile with observations [4, 5]. More recent results show that the crystallization achieved upon solidification of a liquid magma ocean is considerably more complex than previously assumed. In fact, the onset of solid-state convection prior to complete crystallization of the mantle can efficiently reduce mantle chemical heterogeneities [5]. We thus conclude that mantle mixing may partly or even completely erase the effects of fractional crystallization well before complete solidification. Nevertheless, the subsequent differentiation caused by partial melting, may introduce additional heterogeneities between residual and primitive mantle that could explain compositional differences observed over the surface of terrestrial bodies [6]. References: [1] Charlier et al., 2013, EPSL; [2] Elkins-Tanton et al., 2011, EPSL; [3] Elkins-Tanton et al., 2005, JGR; [4] Tosi et al., 2013, JGR; [5] Plesa et al., 2014, EPSL; [5] Maurice et al, 2015, EGU; [6] Plesa & Breuer, 2014, PSS.

Anti-biofilm and anti-adherence activities of sub fraction 18 of Melastoma malabathricum towards Streptococcus mutans

NASA Astrophysics Data System (ADS)

Rohazila M., H.; Nazlina, I.; Yaacob W., A.

2014-09-01

A study was carried out to isolate and identify the active compounds from Melastoma malabathricum stem bark that exhibit anti-biofilm and anti-adherence activities against Streptococcus mutans. Purification of the active compounds from the stem bark extract was performed via silica gel chromatography to produce 12 fractions. Further fractionation of fraction 9 by high performance liquid chromatography (HPLC) produced 21 sub fractions. All the sub fractions were subjected to thin layer chromatography (TLC) bioautography as preliminary screening to determine anti bacterial activity. TLC-bioautography showed that sub fraction 18 (SF18) demonstrated large inhibited zone against S. mutans. Gas chromatography mass spectrometry (GCMS) was used to identify the active compounds in SF18. Fraction SF18 revealed 27 compounds such as hexanoic acid, 8-methyl-1-undecene, propanenitrile, and 1-decene. Anti-biofilm and anti-adherence activities were determined using crystal violet and glass surface assays respectively. The concentrations that produced 50% reduction in anti-biofilm and anti-adherence activities were 1.88 mg/ml and 3.75 mg/ml respectively.

On the Role of Mantle Overturn during Magma Ocean Solidification

NASA Astrophysics Data System (ADS)

Boukaré, C. E.; Parmentier, E.; Parman, S. W.

2017-12-01

Solidification of potential global magma ocean(s) (MO) early in the history of terrestrial planets may play a key role in the evolution of planetary interiors by setting initial conditions for their long-term evolution. Constraining this initial structure of solid mantles is thus crucial but remains poorly understood. MO fractional crystallization has been proposed to generate gravitationally unstable Fe-Mg chemical stratification capable of driving solid-state mantle overturn. Fractional solidification and overturn hypothesis, while only an ideal limiting case, can explain important geochemical features of both the Moon and Mars. Current overturn models consider generally post-MO overturn where the cumulate pile remains immobile until the end of MO solidification. However, if the cumulate pile overturns during MO solidification, the general picture of early planet evolution might differ significantly from the static crystallization models. We show that the timing of mantle overturn can be characterized with a dimensionless number measuring the ratio of the MO solidification time and the purely compositional overturn timescale. Syn-solidification overturn occurs if this dimensionless parameter, Rc, exceeds a critical value. Rc is mostly affected by the competition between the MO solidification time and mantle viscosity. Overturn that occurs during solidification can result in smaller scales of mantle chemical heterogeneity that could persist for long times thus influencing the whole evolution of a planetary body. We will discuss the effects of compaction/percolation on mantle viscosity. If partially molten cumulate do not have time to compact during MO solidification, viscosity of cumulates would be significantly lower as the interstitcial melt fraction would be large. Both solid mantle remelting during syn-solidification overturn and porous convection of melt retained with the cumulates are expected to reduce the degree of fractional crystallization. Syn-solidification overturn of a sluggish mantle can thus be an alternative to solid-state post-MO solidification overturn.

Tensile behavior of laser treated Fe-Si-B metallic glass

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

Joshi, Sameehan S.; Samimi, Peyman; Ghamarian, Iman

2015-10-28

Fe-Si-B metallic glass foils were treated with a linear laser track using a continuous wave Nd-YAG laser and its effect on the overall tensile behavior was investigated. Microstructure and phase evolutions were evaluated using X-ray diffraction, resistivity measurements, and transmission electron microscopy. Crystallization fraction was estimated via the differential scanning calorimetry technique. Metallic glass foils treated with the lower laser fluences (<0.49 J/mm{sup 2}) experienced structural relaxation, whereas higher laser fluences led to crystallization within the laser treated region. The overall tensile behavior was least impacted by structural relaxation, whereas crystallization severely reduced the ultimate tensile strength of the laser treatedmore » metallic glass foils.« less

Preparation and magnetic properties of magnetic photonic crystal by using monodisperse polystyrene covered Fe3O4 nanoparticles onto glass substrate

NASA Astrophysics Data System (ADS)

Azizi, Zahra Sadat; Tehranchi, Mohammad Mehdi; Vakili, Seyed Hamed; Pourmahdian, Saeed

2018-05-01

Engineering approach towards combined photonic band gap properties and magnetic/polymer composite particles, attract considerable attention of researchers due to their unique properties. In this research, two different magnetic particles were prepared by nearly monodisperse polystyrene spheres as bead with two concentrations of Fe3O4 nanoparticles to prepare magnetic photonic crystals (MPCs). The crystal surfaces and particles morphology were investigated employing scanning electron microscopy and transmission electron microscopy. The volume fraction of magnetic material embedded into colloidal spheres and their morphology was found to be a key parameter in the optical and magneto-optical properties of transparent MPC.

A Study of the Optical Properties of Ice Crystals with Black Carbon Inclusions

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

Arienti, Marco; Yang, Xiaoyuan; Kopacz, Adrian M

2015-09-01

The report focu ses on the modification of the optical properties of ice crystals due to atmospheric black car bon (BC) contamination : the objective is to advance the predictive capabilities of climate models through an improved understanding of the radiative properties of compound particles . The shape of the ice crystal (as commonly found in cirrus clouds and cont rails) , the volume fraction of the BC inclusion , and its location inside the crystal are the three factors examined in this study. In the multiscale description of this problem, where a small absorbing inclusion modifies the optical propertiesmore » of a much la rger non - absorbing particle, state - of - the - art discretization techniques are combined to provide the best compromise of flexibility and accuracy over a broad range of sizes .« less

Statistical Analysis of Crystallization Database Links Protein Physico-Chemical Features with Crystallization Mechanisms

PubMed Central

Fusco, Diana; Barnum, Timothy J.; Bruno, Andrew E.; Luft, Joseph R.; Snell, Edward H.; Mukherjee, Sayan; Charbonneau, Patrick

2014-01-01

X-ray crystallography is the predominant method for obtaining atomic-scale information about biological macromolecules. Despite the success of the technique, obtaining well diffracting crystals still critically limits going from protein to structure. In practice, the crystallization process proceeds through knowledge-informed empiricism. Better physico-chemical understanding remains elusive because of the large number of variables involved, hence little guidance is available to systematically identify solution conditions that promote crystallization. To help determine relationships between macromolecular properties and their crystallization propensity, we have trained statistical models on samples for 182 proteins supplied by the Northeast Structural Genomics consortium. Gaussian processes, which capture trends beyond the reach of linear statistical models, distinguish between two main physico-chemical mechanisms driving crystallization. One is characterized by low levels of side chain entropy and has been extensively reported in the literature. The other identifies specific electrostatic interactions not previously described in the crystallization context. Because evidence for two distinct mechanisms can be gleaned both from crystal contacts and from solution conditions leading to successful crystallization, the model offers future avenues for optimizing crystallization screens based on partial structural information. The availability of crystallization data coupled with structural outcomes analyzed through state-of-the-art statistical models may thus guide macromolecular crystallization toward a more rational basis. PMID:24988076

Statistical analysis of crystallization database links protein physico-chemical features with crystallization mechanisms.

PubMed

Fusco, Diana; Barnum, Timothy J; Bruno, Andrew E; Luft, Joseph R; Snell, Edward H; Mukherjee, Sayan; Charbonneau, Patrick

2014-01-01

X-ray crystallography is the predominant method for obtaining atomic-scale information about biological macromolecules. Despite the success of the technique, obtaining well diffracting crystals still critically limits going from protein to structure. In practice, the crystallization process proceeds through knowledge-informed empiricism. Better physico-chemical understanding remains elusive because of the large number of variables involved, hence little guidance is available to systematically identify solution conditions that promote crystallization. To help determine relationships between macromolecular properties and their crystallization propensity, we have trained statistical models on samples for 182 proteins supplied by the Northeast Structural Genomics consortium. Gaussian processes, which capture trends beyond the reach of linear statistical models, distinguish between two main physico-chemical mechanisms driving crystallization. One is characterized by low levels of side chain entropy and has been extensively reported in the literature. The other identifies specific electrostatic interactions not previously described in the crystallization context. Because evidence for two distinct mechanisms can be gleaned both from crystal contacts and from solution conditions leading to successful crystallization, the model offers future avenues for optimizing crystallization screens based on partial structural information. The availability of crystallization data coupled with structural outcomes analyzed through state-of-the-art statistical models may thus guide macromolecular crystallization toward a more rational basis.

Shock and Microstructural Characterization of the α-ω Phase Transition in Titanium Crystals

NASA Astrophysics Data System (ADS)

Morrow, Benjamin M.; Rigg, Paulo A.; Jones, David R.; Addessio, Francis L.; Trujillo, Carl P.; Saavedra, Ramon A.; Martinez, Daniel T.; Cerreta, Ellen K.

2017-12-01

A multicrystal comprised of a small number of large crystals of high-purity titanium and a [0001] oriented high-purity single crystal titanium sample were shock loaded using gas gun plate impact experiments. Tests were performed at stresses above the α {-}ω phase transition stress (for high-purity polycrystalline specimens) to observe the behavior of oriented crystals under similar conditions. Post-mortem characterization of the shocked microstructure was conducted on the single crystal sample to measure textures, and quantify phases and twinning. The apparent activation of plastic and transformation mechanisms was dependent upon crystal orientation. Specifically, the [0001] crystal showed a higher Hugoniot elastic limit than the [10\\bar{1}0] or [3\\bar{1}\\bar{4}4] orientations. The slope of velocity as a function of time was lower in the [0001] orientation than the other orientations during plastic deformation, indicating sluggish transformation kinetics for the α to ω phase transition for the [0001] oriented crystal. Microtexture measurements of a recovered [0001] oriented single crystal revealed the presence of retained ω phase after unloading, with orientations of the constituent phase fractions indicative of the forward α → ω transition, rather than the reverse ω → α transition, suggesting that the material never achieved a state of 100% ω phase.

Real-time observation of the isothermal crystallization kinetics in a deeply supercooled liquid

NASA Astrophysics Data System (ADS)

Zanatta, M.; Cormier, L.; Hennet, L.; Petrillo, C.; Sacchetti, F.

2017-03-01

Below the melting temperature Tm, crystals are the stable phase of typical elemental or molecular systems. However, cooling down a liquid below Tm, crystallization is anything but inevitable. The liquid can be supercooled, eventually forming a glass below the glass transition temperature Tg. Despite their long lifetimes and the presence of strong barriers that produces an apparent stability, supercooled liquids and glasses remain intrinsically a metastable state and thermodynamically unstable towards the crystal. Here we investigated the isothermal crystallization kinetics of the prototypical strong glassformer GeO2 in the deep supercooled liquid at 1100 K, about half-way between Tm and Tg. The crystallization process has been observed through time-resolved neutron diffraction for about three days. Data show a continuous reorganization of the amorphous structure towards the alpha-quartz phase with the final material composed by crystalline domains plunged into a low-density, residual amorphous matrix. A quantitative analysis of the diffraction patterns allows determining the time evolution of the relative fractions of crystal and amorphous, that was interpreted through an empirical model for the crystallization kinetics. This approach provides a very good description of the experimental data and identifies a predator-prey-like mechanism between crystal and amorphous, where the density variation acts as a blocking barrier.

Ferric Iron Production in Magma Oceans and Evolution of Mantle Oxidation State

NASA Astrophysics Data System (ADS)

Schaefer, L.; Elkins-Tanton, L. T.; Pahlevan, K.

2018-05-01

Self-oxidation of the magma ocean by ferric iron production at high pressure may explain the mantle oxidation state of the Earth. Partitioning during fractional crystallization can further increase the mantle oxygen fugacity during solidification.

CUMULATE ROCKS ASSOCIATED WITH CARBONATE ASSIMILATION, HORTAVÆR COMPLEX, NORTH-CENTRAL NORWAY

NASA Astrophysics Data System (ADS)

Barnes, C. G.; Prestvik, T.; Li, Y.

2009-12-01

The Hortavær igneous complex intruded high-grade metamorphic rocks of the Caledonian Helgeland Nappe Complex at ca. 466 Ma. The complex is an unusual mafic-silicic layered intrusion (MASLI) because the principal felsic rock type is syenite and because the syenite formed in situ rather than by deep-seated partial melting of crustal rocks. Magma differentiation in the complex was by assimilation, primarily of calc-silicate rocks and melts with contributions from marble and semi-pelites, plus fractional crystallization. The effect of assimilation of calcite-rich rocks was to enhance stability of fassaitic clinopyroxene at the expense of olivine, which resulted in alkali-rich residual melts and lowering of silica activity. This combination of MASLI-style emplacement and carbonate assimilation produced three types of cumulate rocks: (1) Syenitic cumulates formed by liquid-crystal separation. As sheets of mafic magma were loaded on crystal-rich syenitic magma, residual liquid was expelled, penetrating the overlying mafic sheets in flame structures, and leaving a cumulate syenite. (2) Reaction cumulates. Carbonate assimilation, illustrated by a simple assimilation reaction: olivine + calcite + melt = clinopyroxene + CO2 resulted in cpx-rich cumulates such as clinopyroxenite, gabbro, and mela-monzodiorite, many of which contain igneous calcite. (3) Magmatic skarns. Calc-silicate host rocks underwent partial melting during assimilation, yielding a Ca-rich melt as the principal assimilated material and permitting extensive reaction with surrounding magma to form Kspar + cpx + garnet-rich ‘cumulate’ rocks. Cumulate types (2) and (3) do not reflect traditional views of cumulate rocks but instead result from a series of melt-present discontinuous (peritectic) reactions and partial melting of calc-silicate xenoliths. In the Hortavær complex, such cumulates are evident because of the distinctive peritectic cumulate assemblages. It is unclear whether assimilation of ‘normal’ silicate rocks results in peritectic assemblages, or whether they could be identified as such if they exist.

(U-Th-Sm)/He thermochronological age distribution in a slowly cooled plutonic complex (Ploumanac'h intrusion, France): insights into helium diffusion processes.

NASA Astrophysics Data System (ADS)

Recanati, A. C.; Gautheron, C.; Barbarand, J.; Tassan-Got, L.; Missenard, Y.; Pinna-Jamme, R.

2015-12-01

(U-Th-Sm)/He thermochronology is widely used to determine the thermal histories of mountain ranges and sedimentary basins. Apatite crystals retain helium at low temperatures, thus giving an insight into upper crustal evolution (e.g. exhumation, subsidence, erosion). Advanced models predict He production and diffusion rates in apatite crystals, thereby allowing determination of helium dates by integration over time/temperature paths (e.g. Gautheron et al., 2009). However, scattered dates and discordance between predicted and measured dates suggest that other parameters than time or temperature may also influence helium contents in apatite. The present study determines the variables that affect He diffusion in apatite over long timescales. We report the (U-Th-Sm)/He date distribution within a slowly cooled intrusion, along with AFT data, as well as extensive petrological and chemical characterization. The Ploumanac'h site (Brittany, France) was chosen because it includes small-scale spatial variations in petrology and chemistry (6-9106 tracks/cm2). GAUTHERON C., TASSAN-GOT L., BARBARAND J., PAGEL M., 2009. Effect of alpha-damage annealing on apatite (U-Th)/He thermochronology. Chem. Geol. 266, 166-179.

Discerning crystal growth from diffusion profiles in zoned olivine by in situ Mg–Fe isotopic analyses

USGS Publications Warehouse

Sio, Corliss Kin I.; Dauphas, Nicolas; Teng, Fang-Zhen; Chaussidon, Marc; Helz, Rosalind T.; Roskosz, Mathieu

2013-01-01

Mineral zoning is used in diffusion-based geospeedometry to determine magmatic timescales. Progress in this field has been hampered by the challenge to discern mineral zoning produced by diffusion from concentration gradients inherited from crystal growth. A zoned olivine phenocryst from Kilauea Iki lava lake (Hawaii) was selected for this study to evaluate the potential of Mg and Fe isotopes for distinguishing these two processes. Microdrilling of the phenocryst (∼300 μm drill holes) followed by MC-ICPMS analysis of the powders revealed negatively coupled Mg and Fe isotopic fractionations (δ26Mg from +0.1‰ to −0.2‰ and δ56Fe from −1.2‰ to −0.2‰ from core to rim), which can only be explained by Mg–Fe exchange between melt and olivine. The data can be explained with ratios of diffusivities of Mg and Fe isotopes in olivine scaling as D2/D1 = (m1/m2)β with βMg ∼0.16 and βFe ∼0.27. LA-MC-ICPMS and MC-SIMS Fe isotopic measurements are developed and are demonstrated to yield accurate δ56Fe measurements within precisions of ∼0.2‰ (1 SD) at spatial resolutions of ∼50 μm. δ56Fe and δ26Mg stay constant with Fo# in the rim (late-stage overgrowth), whereas in the core (original phenocryst) δ56Fe steeply trends toward lighter compositions and δ26Mg trends toward heavier compositions with higher Fo#. A plot of δ56Fe vs. Fo# immediately distinguishes growth-controlled from diffusion-controlled zoning in these two regions. The results are consistent with the idea that large isotopic fractionation accompanies chemical diffusion in crystals, whereas fractional crystallization induces little or no isotopic fractionation. The cooling timescale inferred from the chemical-isotope zoning profiles is consistent with the documented cooling history of the lava lake. In the absence of geologic context, in situ stable isotopic measurements may now be used to interpret the nature of mineral zoning. Stable isotope measurements by LA-MC-ICPMS and MC-SIMS can be used as standard petrologic tools to identify samples for diffusion-based geospeedometry.

Expertise in Mathematics Instruction: Subject Matter Knowledge.

ERIC Educational Resources Information Center

Leinhardt, Gaea; Smith, Donald

The relationship between expert teachers' classroom behavior and their subject matter knowledge is an area of research that has not been examined extensively. To begin that study, one topic, fraction knowledge, was explored in depth as it occurred in natural teaching settings. Fractions are one of the more difficult topics in elementary…

Following DNA chain extension and protein conformational changes in crystals of a Y-family DNA polymerase via Raman crystallography.

PubMed

Espinoza-Herrera, Shirly J; Gaur, Vineet; Suo, Zucai; Carey, Paul R

2013-07-23

Y-Family DNA polymerases are known to bypass DNA lesions in vitro and in vivo. Sulfolobus solfataricus DNA polymerase (Dpo4) was chosen as a model Y-family enzyme for investigating the mechanism of DNA synthesis in single crystals. Crystals of Dpo4 in complexes with DNA (the binary complex) in the presence or absence of an incoming nucleotide were analyzed by Raman microscopy. (13)C- and (15)N-labeled d*CTP, or unlabeled dCTP, were soaked into the binary crystals with G as the templating base. In the presence of the catalytic metal ions, Mg(2+) and Mn(2+), nucleotide incorporation was detected by the disappearance of the triphosphate band of dCTP and the retention of *C modes in the crystal following soaking out of noncovalently bound C(or *C)TP. The addition of the second coded base, thymine, was observed by adding cognate dTTP to the crystal following a single d*CTP addition. Adding these two bases caused visible damage to the crystal that was possibly caused by protein and/or DNA conformational change within the crystal. When d*CTP is soaked into the Dpo4 crystal in the absence of Mn(2+) or Mg(2+), the primer extension reaction did not occur; instead, a ternary protein·template·d*CTP complex was formed. In the Raman difference spectra of both binary and ternary complexes, in addition to the modes of d(*C)CTP, features caused by ring modes from the template/primer bases being perturbed and from the DNA backbone appear, as well as features from perturbed peptide and amino acid side chain modes. These effects are more pronounced in the ternary complex than in the binary complex. Using standardized Raman intensities followed as a function of time, the C(*C)TP population in the crystal was maximal at ∼20 min. These remained unchanged in the ternary complex but declined in the binary complexes as chain incorporation occurred.

Effect of doping of KDP crystal with amino acid L-arginine on the strength properties and character of laser damage

NASA Astrophysics Data System (ADS)

Dolzhenkova, E. F.; Kostenyukova, E. I.; Bezkrovnaya, O. N.; Pritula, I. M.

2017-11-01

Studied were the strength characteristics of KDP crystals doped with L-arginine under a concentrated load and irradiation of the first harmonic YAG:Nd3+ laser. The crystals were obtained by means of the temperature reduction method on a point seed, the content of L-arginine in the aqueous solution being 0.3, 0.4, 1.0 and 1.4 wt%. The character of the dependence of KDP microhardness versus the concentration of amino acid in the crystal was investigated. The regularities of brittle damage of the doped KDP crystal at mechanical testing and laser irradiation were shown to be similar. As confirmed in the study, the planes of easy crack extension in the crystal are {2 2 1}, (1 0 0), and (0 0 1) planes, the cracks mainly propagate parallel to {2 2 1} planes. The mechanical and laser strength values of doped KDP crystals were evaluated.

The Biomolecular Crystallization Database Version 4: expanded content and new features.

PubMed

Tung, Michael; Gallagher, D Travis

2009-01-01

The Biological Macromolecular Crystallization Database (BMCD) has been a publicly available resource since 1988, providing a curated archive of information on crystal growth for proteins and other biological macromolecules. The BMCD content has recently been expanded to include 14 372 crystal entries. The resource continues to be freely available at http://xpdb.nist.gov:8060/BMCD4. In addition, the software has been adapted to support the Java-based Lucene query language, enabling detailed searching over specific parameters, and explicit search of parameter ranges is offered for five numeric variables. Extensive tools have been developed for import and handling of data from the RCSB Protein Data Bank. The updated BMCD is called version 4.02 or BMCD4. BMCD4 entries have been expanded to include macromolecule sequence, enabling more elaborate analysis of relations among protein properties, crystal-growth conditions and the geometric and diffraction properties of the crystals. The BMCD version 4.02 contains greatly expanded content and enhanced search capabilities to facilitate scientific analysis and design of crystal-growth strategies.

Temporal Evolution of Volcanic and Plutonic Magmas Related to Porphyry Copper Ores Based on Zircon Geochemistry

NASA Astrophysics Data System (ADS)

Dilles, J. H.; Lee, R. G.; Wooden, J. L.; Koleszar, A. M.

2015-12-01

Porphyry Cu (Mo-Au) and epithermal Au-Ag ores are globally associated with shallow hydrous, strongly oxidized, and sulfur-rich arc intrusions. In many localities, long-lived magmatism includes evolution from early andesitic volcanic (v) and plutonic (p) rocks to later dacitic or rhyolitic compositions dominated by plutons. We compare zircon compositions from three igneous suites with different time spans: Yerington, USA (1 m.y., p>v), El Salvador, Chile (4 m.y., p>v), and Yanacocha, Peru (6 m.y., v>p). At Yerington granite dikes and ores formed in one event, at ES in 2 to 3 events spanning 3 m.y., and at Yanacocha in 6 events spanning 5 m.y. At both ES and Yanacocha, high-Al amphiboles likely crystallized at high temperature in the mid-crust and attest to deep magmas that periodically recharged the shallow chambers. At Yanacocha, these amphiboles contain anhydrite inclusions that require magmas were sulfur-rich and strongly oxidized (~NNO+2). The Ti-in-zircon geothermometer provides estimates of 920º to 620º C for zircon crystallization, and records both core to rim cooling and locally high temperature rim overgrowths. Ore-related silicic porphyries yield near-solidus crystallization temperatures of 750-650°C consistent with low zircon saturation temperatures. The latter zircons have large positive Ce/Ce* and small negative Eu/Eu*≥0.4 anomalies attesting to strongly oxidized conditions (Ballard et al., 2001), which we propose result from crystallization and SO2 loss to the magmatic-hydrothermal ore fluid (Dilles et al., 2015). The Hf, REE, Y, U, and Th contents of zircons are diverse in the magma suites, and Th/U vs Yb/Gd plots suggest a dominant role of crystal fractionation with lesser roles for both crustal contamination and mixing with high temperature deep-sourced mafic magma. Ce/Sm vs Yb/Gd plots suggest that magma REE contents at <900°C are dominated by early crystallization of hornblende and apatite, and late crystallization (~<780°C) of titanite. Magma mixing and crustal contamination are most evident in pre-ore magmas, whereas ore-forming intrusions at low temperatures are dominated by crystal fractionation. Thus, zircon provides evidence for cyclic crystallization and mafic recharge that enrich late silicic melts in incompatible ore components water, sulfur, chlorine and metals.

Evaluation of terrestrial plants extracts for uranium sorption and characterization of potent phytoconstituents.

PubMed

Sharma, Sunita; Singh, Bikram; Thulasidas, S K; Kulkarni, Madhuri J; Natarajan, V; Manchanda, Vijay K

2016-01-01

Sorption capacity of four plants (Funaria hygrometrica, Musa acuminata, Brassica juncea and Helianthus annuus) extracts/fractions for uranium, a radionuclide was investigated by EDXRF and tracer studies. The maximum sorption capacity, i.e., 100% (complete sorption) was observed in case of Musa acuminata extract and fractions. Carbohydrate, proteins, phenolics and flavonoids contents in the active fraction (having maximum sorption capacity) were also determined. Further purification of the most active fraction provided three pure molecules, mannitol, sorbitol and oxo-linked potassium oxalate. The characterization of isolated molecules was achieved by using FTIR, NMR, GC-MS, MS-MS, and by single crystal-XRD analysis. Of three molecules, oxo-linked potassium oxalate was observed to have 100% sorption activity. Possible binding mechanism of active molecule with the uranyl cation has been purposed.

Proceedings of the NATO Advances Research Workshop on Diamond Based Composites, Saint Petersburg, Russia, June 21-22, 1997, Volume 38

DTIC Science & Technology

1997-06-01

composites. The topics ranged from molecular clusters, nanophase materials, growth, processing, and synthesis. Commercial composite materials have been on...example, an analysis of the emission from a GaAs target shows mainly (99.4%) neutral Ga and As atoms. [63] However, the fraction of molecular species...sputtered from ionic crystals can be considerably higher. [64] There is evidence that a large fraction of the molecular species originate from

Extensions of different type parameterized inequalities for generalized [Formula: see text]-preinvex mappings via k-fractional integrals.

PubMed

Zhang, Yao; Du, Ting-Song; Wang, Hao; Shen, Yan-Jun; Kashuri, Artion

2018-01-01

The authors discover a general k -fractional integral identity with multi-parameters for twice differentiable functions. By using this integral equation, the authors derive some new bounds on Hermite-Hadamard's and Simpson's inequalities for generalized [Formula: see text]-preinvex functions through k -fractional integrals. By taking the special parameter values for various suitable choices of function h , some interesting results are also obtained.

Thermal crystallization mechanism of silk fibroin protein

NASA Astrophysics Data System (ADS)

Hu, Xiao

In this thesis, the thermal crystallization mechanism of silk fibroin protein from Bombyx mori silkworm, was treated as a model for the general study of protein based materials, combining theories from both biophysics and polymer physics fields. A systematic and scientific path way to model the dynamic beta-sheet crystallization process of silk fibroin protein was presented in the following sequence: (1) The crystallinity, fractions of secondary structures, and phase compositions in silk fibroin proteins at any transition stage were determined. Two experimental methods, Fourier transform infrared spectroscopy (FTIR) with Fourier self-deconvolution, and specific reversing heat capacity, were used together for the first time for modeling the static structures and phases in the silk fibroin proteins. The protein secondary structure fractions during the crystallization were quantitatively determined. The possibility of existence of a "rigid amorphous phase" in silk protein was also discussed. (2) The function of bound water during the crystallization process of silk fibroin was studied using heat capacity, and used to build a silk-water dynamic crystallization model. The fundamental concepts and thermal properties of silk fibroin with/without bound water were discussed. Results show that intermolecular bound water molecules, acting as a plasticizer, will cause silk to display a water-induced glass transition around 80°C. During heating, water is lost, and the change of the microenvironment in the silk fibroin chains induces a mesophase prior to thermal crystallization. Real time FTIR during heating and isothermal holding above Tg show the tyrosine side chain changes only during the former process, while beta sheet crystallization occurs only during the latter process. Analogy is made between the crystallization of synthetic polymers according to the four-state scheme of Strobl, and the crystallization process of silk fibroin, which includes an intermediate precursor stage before crystallization. (3) The beta-sheet crystallization kinetics in silk fibroin protein were measured using X-ray, FTIR and heat flow, and the structure reveals the formation mechanism of the silk crystal network. Avrami kinetics theories, which were established for studies of synthetic polymer crystal growth, were for the first time extended to investigate protein self-assembly in multiblock silk fibroin samples. The Avrami exponent, n, was close to two for all methods, indicating formation of beta sheet crystals in silk proteins is different from the 3-D spherulitic crystal growth found in most synthetic homopolymers. A microphase separation pattern after chymotrypsin enzyme biodegradation was shown in the protein structures using scanning electron microscopy. A model was then used to explain the crystallization of silk fibroin protein by analogy to block copolymers. (4) The effects of metal ions during the crystallization of silk fibroin was investigated using thermal analysis. Advanced thermal analysis methods were used to analyze the thermal protein-metallic ion interactions in silk fibroin proteins. Results show that K+ and Ca2+ metallic salts play different roles in silk fibroin proteins, which either reduce (K+) or increase (Ca2+ ) the glass transition (Tg) of pure silk protein and affect the thermal stability of this structure.

Oligocene ash flow volcanism, northern Sierra Madre Occidental: Role of mafic and intermediate-composition magmas in rhyolite genesis

NASA Astrophysics Data System (ADS)

Wark, David A.

1991-07-01

Field, geochemical, and isotopic data from the Tomochic volcanic center in Chihuahua, Mexico, are interpreted to indicate a genetic relationship between large-volume rhyolite ash-flow tuffs and associated more mafic lithologies. These lithologies include (1) porphyritic, two-pyroxene andesite (>35 Ma) that was extruded mostly before ash-flow volcanism, and (2) crystal-poor basaltic andesite that was erupted mostly after ash-flow activity (˜30 Ma) but which was also extruded earlier (˜34 Ma) with hybrid intracaldera lavas. Major silicic units at Tomochic include the Vista (˜34 Ma) and Rio Verde (˜32 Ma) rhyolite ash-flow tuffs; also present are ash-flow tuffs (˜38, 36, and 29 Ma) erupted from other sources. A model of rhyolite genesis by closed-system crystal fractionation of andesite is consistent with geochemical and isotopic data. The least evolved Vista rhyolite was formed by fractionation of ˜65% the original mass of andesite; an additional ˜55% fractionation of plagioclase, alkali feldspar, quartz, biotite, hornblende, FeTi oxides, and sphene generated the most evolved Vista sample. Rio Verde rhyolites were generated from andesite by ˜50% mass fractionation of an assemblage dominated by plagioclase, pyroxene, and FeTi oxides. Initial Nd and Sr isotope ratios of andesite-dacite lavas (ɛNd = -2.3 to -5.2; 87Sr/86Sr = 0.7060 to 0.7089) and of rhyolites (ɛNd = +0.5 to -2.7; 87Sr/86Sr = 0.7053 to 0.7066) partly overlap and extend from values near the mantle array toward values typical of old continental crust on an ɛNd-87Sr/86Sr diagram. These isotope ratios, which do not correlate with indices of differentiation, are interpreted to indicate that parental andesite already contained a crustal component (possibly >20%) before fractionation to rhyolite. The isotopic and geochemical signatures of andesites apparently reflect the incorporation of crust by subduction-related, mafic melts represented by (but more primitive than) exposed basaltic andesites, which have isotope ratios (ɛNd = +1.0 to -0.1; 87Sr/86Sr = 0.7044 to 0.7053) near "bulk earth". The pattern of volcanic evolution at the Tomochic center, specifically the transition from andesitic to rhyolite dominated, with late extrusion of basaltic andesite, also occurred in other parts of the volcanic field, and roughly coincided with a sharp decrease in the rate of Farallon plate subduction. This change in subduction rate apparently resulted in a decreased flux of mafic melts into the crust from below, and was associated with the onset of crustal extension and hence, shorter residence times for mafic melts formerly ponded in the deep crust These, in turn, resulted in (1) the change from andesitic to rhyolite-dominated volcanism as ascending intermediate-composition magmas stalled, coalesced, and differentiated to produce rhyolite, (2) extrusion of basaltic andesite upon brittle failure of the shallow crust, and (3) subsequent termination of calc-alkalic volcanism throughout the Sierra Madre Occidental.

On the Singular Perturbations for Fractional Differential Equation

PubMed Central

Atangana, Abdon

2014-01-01

The goal of this paper is to examine the possible extension of the singular perturbation differential equation to the concept of fractional order derivative. To achieve this, we presented a review of the concept of fractional calculus. We make use of the Laplace transform operator to derive exact solution of singular perturbation fractional linear differential equations. We make use of the methodology of three analytical methods to present exact and approximate solution of the singular perturbation fractional, nonlinear, nonhomogeneous differential equation. These methods are including the regular perturbation method, the new development of the variational iteration method, and the homotopy decomposition method. PMID:24683357

Crystal morphology optimization of thiamine hydrochloride in solvent system: Experimental and molecular dynamics simulation studies

NASA Astrophysics Data System (ADS)

Yang, Yang; Han, Dandan; Du, Shichao; Wu, Songgu; Gong, Junbo

2018-01-01

Thiamine hydrochloride (THCL) was produced in methanol accompanied with agglomeration in industry, the plate like morphology of THCL in methanol was not deserve to have a good quality. Selecting a suitable solvent should be considered because solvent could be one of the essential factors to impact morphology. Methanol and methanol/ethyl acetate solvent (0.2 vol fraction of methanol) was selected as the solvent system in reactive crystallization of THCL. The experiment results show the THCL crystal morphology in methanol/ethyl acetate solvent system was granular and more regular than that in methanol. In order to explicate the different crystal morphology in different solvents, molecular dynamics (MD) simulation was introduced to simulate crystal morphology in different solvents. The attachment energy (AE) model was employed to investigate the morphology of THCL under vacuum conditions, methanol and methanol/ethyl acetate solvent conditions, respectively. The simulation crystal morphology was in a good agreement with that of experimented. The particle of THCL in methanol/ethyl acetate solvent has less tendency to agglomeration, and then it is favorable to the downstream process, such as filtration, storage and transportation.

The Surface Structure of Ground Metal Crystals

NASA Technical Reports Server (NTRS)

Boas, W.; Schmid, E.

1944-01-01

The changes produced on metallic surfaces as a result of grinding and polishing are not as yet fully understood. Undoubtedly there is some more or less marked change in the crystal structure, at least, in the top layer. Hereby a diffusion of separated crystal particles may be involved, or, on plastic material, the formation of a layer in greatly deformed state, with possible recrystallization in certain conditions. Czochralski verified the existence of such a layer on tin micro-sections by successive observations of the texture after repeated etching; while Thomassen established, roentgenographically by means of the Debye-Scherrer method, the existence of diffused crystal fractions on the surface of ground and polished tin bars, which he had already observed after turning (on the lathe). (Thickness of this layer - 0.07 mm). Whether this layer borders direct on the undamaged base material or whether deformed intermediate layers form the transition, nothing is known. One observation ty Sachs and Shoji simply states that after the turning of an alpha-brass crystal the disturbance starting from the surface, penetrates fairly deep (approx. 1 mm) into the crystal (proof by recrystallization at 750 C).

Microfluidic sorting of protein nanocrystals by size for X-ray free-electron laser diffraction

PubMed Central

Abdallah, Bahige G.; Zatsepin, Nadia A.; Roy-Chowdhury, Shatabdi; Coe, Jesse; Conrad, Chelsie E.; Dörner, Katerina; Sierra, Raymond G.; Stevenson, Hilary P.; Camacho-Alanis, Fernanda; Grant, Thomas D.; Nelson, Garrett; James, Daniel; Calero, Guillermo; Wachter, Rebekka M.; Spence, John C. H.; Weierstall, Uwe; Fromme, Petra; Ros, Alexandra

2015-01-01

The advent and application of the X-ray free-electron laser (XFEL) has uncovered the structures of proteins that could not previously be solved using traditional crystallography. While this new technology is powerful, optimization of the process is still needed to improve data quality and analysis efficiency. One area is sample heterogeneity, where variations in crystal size (among other factors) lead to the requirement of large data sets (and thus 10–100 mg of protein) for determining accurate structure factors. To decrease sample dispersity, we developed a high-throughput microfluidic sorter operating on the principle of dielectrophoresis, whereby polydisperse particles can be transported into various fluid streams for size fractionation. Using this microsorter, we isolated several milliliters of photosystem I nanocrystal fractions ranging from 200 to 600 nm in size as characterized by dynamic light scattering, nanoparticle tracking, and electron microscopy. Sorted nanocrystals were delivered in a liquid jet via the gas dynamic virtual nozzle into the path of the XFEL at the Linac Coherent Light Source. We obtained diffraction to ∼4 Å resolution, indicating that the small crystals were not damaged by the sorting process. We also observed the shape transforms of photosystem I nanocrystals, demonstrating that our device can optimize data collection for the shape transform-based phasing method. Using simulations, we show that narrow crystal size distributions can significantly improve merged data quality in serial crystallography. From this proof-of-concept work, we expect that the automated size-sorting of protein crystals will become an important step for sample production by reducing the amount of protein needed for a high quality final structure and the development of novel phasing methods that exploit inter-Bragg reflection intensities or use variations in beam intensity for radiation damage-induced phasing. This method will also permit an analysis of the dependence of crystal quality on crystal size. PMID:26798818

Microfluidic sorting of protein nanocrystals by size for X-ray free-electron laser diffraction

DOE PAGES

Abdallah, Bahige G.; Zatsepin, Nadia A.; Roy-Chowdhury, Shatabdi; ...

2015-08-19

We report that the advent and application of the X-ray free-electron laser (XFEL) has uncovered the structures of proteins that could not previously be solved using traditional crystallography. While this new technology is powerful, optimization of the process is still needed to improve data quality and analysis efficiency. One area is sample heterogeneity, where variations in crystal size (among other factors) lead to the requirement of large data sets (and thus 10–100 mg of protein) for determining accurate structure factors. To decrease sample dispersity, we developed a high-throughput microfluidic sorter operating on the principle of dielectrophoresis, whereby polydisperse particles canmore » be transported into various fluid streams for size fractionation. Using this microsorter, we isolated several milliliters of photosystem I nanocrystal fractions ranging from 200 to 600 nm in size as characterized by dynamic light scattering, nanoparticle tracking, and electron microscopy. Sorted nanocrystals were delivered in a liquid jet via the gas dynamic virtual nozzle into the path of the XFEL at the Linac Coherent Light Source. We obtained diffraction to ~4 Å resolution, indicating that the small crystals were not damaged by the sorting process. We also observed the shape transforms of photosystem I nanocrystals, demonstrating that our device can optimize data collection for the shape transform-based phasing method. Using simulations, we show that narrow crystal size distributions can significantly improve merged data quality in serial crystallography. From this proof-of-concept work, we expect that the automated size-sorting of protein crystals will become an important step for sample production by reducing the amount of protein needed for a high quality final structure and the development of novel phasing methods that exploit inter-Bragg reflection intensities or use variations in beam intensity for radiation damage-induced phasing. Ultimately, this method will also permit an analysis of the dependence of crystal quality on crystal size.« less

Experimental Constraints on a Vesta Magma Ocean

NASA Technical Reports Server (NTRS)

Hoff, C.; Jones, J. H.; Le, L.

2014-01-01

A magma ocean model was devised to relate eucrites (basalts) and diogenites (orthopyroxenites), which are found mixed together as clasts in a suite of polymict breccias known as howardites. The intimate association of eucritic and diogenitic clasts in howardites argues strongly that these three classes of achondritic meteorites all originated from the same planetoid. Reflectance spectral evidence (including that from the DAWN mission) has long suggested that Vesta is indeed the Eucrite Parent Body. Specifically, the magma ocean model was generated as follows: (i) the bulk Vesta composition was taken to be 0.3 CV chondrite + 0.7 L chondrite but using only 10% of the Na2O from this mixture; (ii) this composition is allowed to crystallize at 500 bar until approx. 80% of the system is solid olivine + low-Ca pyroxene; (iii) the remaining 20% liquid crystallizes at one bar from 1250C to 1110C, a temperature slightly above the eucrite solidus. All crystallization calculations were performed using MELTS. In this model, diogenites are produced by cocrystallization of olivine and pyroxene in the >1250C temperature regime, with Main Group eucrite liquids being generated in the 1300-1250C temperature interval. Low-Ca pyroxene reappears at 1210C in the one-bar calculations and fractionates the residual liquid to produce evolved eucrite compositions (Stannern Trend). We have attempted to experimentally reproduce the <1250C portion of the MELTS Vesta magma ocean. In the MELTS calculation, the change from 500 bar to one bar results in a shift of the olivine:low-Ca pyroxene boundary so that the 1250C liquid is now in the olivine field and, consequently, olivine should be the first-crystallizing phase, followed by low-Ca pyroxene at 1210C, and plagioclase at 1170C. Because at one bar the olivine:low-Ca pyroxene boundary is a peritectic, fractional crystallization of the 1210C liquid proceeds with only pyroxene crystallization until plagioclase appears. Thus, the predictions of the MELTS calculation are clear and straightforward.

K-Ar dating and delta O-18-delta D characterization of nanometric illite from Ordovician K-bentonites of the Appalachians: illitization and the Acadian-Alleghenian tectonic activity

USGS Publications Warehouse

Clauer, Norbert; Fallick, Anthony E.; Eberl, Dennis D.; Honty, Miroslav; Huff, Warren D.; Auberti, Amelie

2013-01-01

Nanometric (2 diagram that illitization occurred in all fractions by simultaneous nucleation and crystal growth, except for one sample. In that sample, a period of growth without nucleation was detected on top of the nucleation and growth episode. The K-Ar ages organize into two isochrons, the first at 319.9 ± 2.0 Ma with an initial 40Ar/36Ar ratio of 271 ± 66 Ma, and the second at 284.9 ± 1.2 Ma with an initial 40Ar/36Ar ratio of 310 ± 44. One data point above the older isochron and three between the two isochrons suggest a detrital contamination for the former separate and a possible further generation of nanoparticles for the three others. The samples with the older crystallization age consist of illite and illite-rich mixed-layers, and those with the younger age contain smectite-rich mixed-layers without illite, or illite-enriched illite-smectite mixed-layers. The K-Ar ages fit the age trends published previously for similar K-bentonites with regional age patterns between 240 and 270 Ma in the southwestern region, between 270 and 300 Ma in the central zone and the southern Appalachians, and between 315 and 370 Ma in the northernmost. Each of the two generations of illite crystals yields very consistent δ18O (V-SMOW) values at 17 ± 1‰ for the older and at 21 ± 1‰ for the younger. If crystallization temperatures of the nanometric illite were between 100 and 200 °C, as suggested by microthermometric determinations, the hydrothermal fluids had δ18O values of 4 ± 1‰ in the Dalton district and of 8 ± 1‰ in the Lafayette, Trenton, and Dirtseller districts at 100 °C, and of 11 ± 1 and 15 ± 1‰ in the same locations at 200 °C, probably because the water-rock isotope exchanges at elevated temperature occurred in rock-dominated systems. The δ18O of the fluids remained unchanged during local crystal growth, but varied depending on the geographic location of the samples and timing of illitization. The δD (V-SMOW) values of the different size fractions do not provide consistent information; they range from −70 to −45‰ for most nanometric and micrometric fractions (V-SMOW), but with no apparent coherent pattern. Nanometric illite-rich crystals from K-bentonite that underwent tectono-thermal alteration yield constant ages, constant clay mineralogy, constant crystallite size distributions for all of the nucleating and growing illite-type crystals of each sample, as well as constant δ18O values implying constant fluid chemistry, all pointing to geologically sudden crystallization.

Conserved Binding Mode of Human [beta subscript 2] Adrenergic Receptor Inverse Agonists and Antagonist Revealed by X-ray Crystallography

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

Wacker, Daniel; Fenalti, Gustavo; Brown, Monica A.

2010-11-15

G protein-coupled receptors (GPCRs) represent a large fraction of current pharmaceutical targets, and of the GPCRs, the {beta}{sub 2} adrenergic receptor ({beta}{sub 2}AR) is one of the most extensively studied. Previously, the X-ray crystal structure of {beta}{sub 2}AR has been determined in complex with two partial inverse agonists, but the global impact of additional ligands on the structure or local impacts on the binding site are not well-understood. To assess the extent of such ligand-induced conformational differences, we determined the crystal structures of a previously described engineered {beta}{sub 2}AR construct in complex with two inverse agonists: ICI 118,551 (2.8 {angstrom}),more » a recently described compound (2.8 {angstrom}) (Kolb et al, 2009), and the antagonist alprenolol (3.1 {angstrom}). The structures show the same overall fold observed for the previous {beta}{sub 2}AR structures and demonstrate that the ligand binding site can accommodate compounds of different chemical and pharmacological properties with only minor local structural rearrangements. All three compounds contain a hydroxy-amine motif that establishes a conserved hydrogen bond network with the receptor and chemically diverse aromatic moieties that form distinct interactions with {beta}{sub 2}AR. Furthermore, receptor ligand cross-docking experiments revealed that a single {beta}{sub 2}AR complex can be suitable for docking of a range of antagonists and inverse agonists but also indicate that additional ligand-receptor structures may be useful to further improve performance for in-silico docking or lead-optimization in drug design.« less

Convection and crystal settling in sills

NASA Astrophysics Data System (ADS)

Gibb, Fergus G. F.; Henderson, C. Michael B.

1992-02-01

It has been advocated that convective and crystal settling processes play significant, and perhaps crucial, roles in magmatic differentiation. The fluid dynamics of magma chambers have been extensively studied in recent years, both theoretically and experimentally, but there is disagreement over the nature and scale of the convection, over its bearing on fractionation and possibly over whether it occurs at all. The differential distribution of modal olivine with height in differentiated alkaline basic sills provides critical evidence to resolve this controversy, at least for small to medium-large magma chambers. Our own and others' published data for such sills show that, irrespective of overall olivine content, modal olivine contents tend to increase in a roughly symmetrical manner inwards from the upper and lower margins of the sill, i.e. the distribution patterns are more often approximately D-shaped rather than the classic S-shape generally ascribed to gravity settling. We concur with the majority of other authors that this is an original feature of the filling process which has survived more or less unchanged since emplacement. We therefore conclude that the magmas have not undergone turbulent convection and that gravity settling has usually played only a minor modifying role since the intrusion of these sills. We offer a possible explanation for the apparent contradiction between fluid dynamical theory and the petrological evidence by suggesting that such sills rarely fill by the rapid injection of a single pulse of magma. Rather, they form from a series of pulses or a continuous pulsed influx over a protracted interval during which marginal cooling severely limits the potential for thermal convection.

Investigating the atomic level influencing factors of glass forming ability in NiAl and CuZr metallic glasses

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

Sedighi, Sina; Kirk, Donald Walter; Singh, Chandra Veer, E-mail: chandraveer.singh@utoronto.ca

2015-09-21

Bulk metallic glasses are a relatively new class of amorphous metal alloy which possess unique mechanical and magnetic properties. The specific concentrations and combinations of alloy elements needed to prevent crystallization during melt quenching remains poorly understood. A correlation between atomic properties that can explain some of the previously identified glass forming ability (GFA) anomalies of the NiAl and CuZr systems has been identified, with these findings likely extensible to other transition metal–transition metal and transition metal–metalloid (TM–M) alloy classes as a whole. In this work, molecular dynamics simulation methods are utilized to study thermodynamic, kinetic, and structural properties ofmore » equiatomic CuZr and NiAl metallic glasses in an attempt to further understand the underlying connections between glass forming ability, nature of atomic level bonding, short and medium range ordering, and the evolution of structure and relaxation properties in the disordered phase. The anomalous breakdown of the fragility parameter as a useful GFA indicator in TM–M alloy systems is addressed through an in-depth investigation of bulk stiffness properties and the evolution of (pseudo)Gruneisen parameters over the quench domain, with the efficacy of other common glass forming ability indicators similarly being analyzed through direct computation in respective CuZr and NiAl systems. Comparison of fractional liquid-crystal density differences in the two systems revealed 2-3 times higher values for the NiAl system, providing further support for its efficacy as a general purpose GFA indicator.« less

Controlled crystallization of the lipophilic drug fenofibrate during freeze-drying: elucidation of the mechanism by in-line Raman spectroscopy.

PubMed

de Waard, Hans; De Beer, Thomas; Hinrichs, Wouter L J; Vervaet, Chris; Remon, Jean-Paul; Frijlink, Henderik W

2010-12-01

We developed a novel process, "controlled crystallization during freeze-drying" to produce drug nanocrystals of poorly water-soluble drugs. This process involves freeze-drying at a relatively high temperature of a drug and a matrix material from a mixture of tertiary butyl alcohol and water, resulting in drug nanocrystals incorporated in a matrix. The aim of this study was to elucidate the mechanisms that determine the size of the drug crystals. Fenofibrate was used as a model lipophilic drug. To monitor the crystallization during freeze-drying, a Raman probe was placed just above the sample in the freeze-dryer. These in-line Raman spectroscopy measurements clearly revealed when the different components crystallized during freeze-drying. The solvents crystallized only during the freezing step, while the solutes only crystallized after the temperature was increased, but before drying started. Although the solutes crystallized only after the freezing step, both the freezing rate and the shelf temperature were critical parameters that determined the final crystal size. At a higher freezing rate, smaller interstitial spaces containing the freeze-concentrated fraction were formed, resulting in smaller drug crystals (based on dissolution data). On the other hand, when the solutes crystallized at a lower shelf temperature, the degree of supersaturation is higher, resulting in a higher nucleation rate and consequently more and therefore smaller crystals. In conclusion, for the model drug fenofibrate, a high freezing rate and a relatively low crystallization temperature resulted in the smallest crystals and therefore the highest dissolution rate.

Smart window using a thermally and optically switchable liquid crystal cell

NASA Astrophysics Data System (ADS)

Oh, Seung-Won; Kim, Sang-Hyeok; Baek, Jong-Min; Yoon, Tae-Hoon

2018-02-01

Light shutter technologies that can control optical transparency have been studied extensively for developing curtain-free smart windows. We introduce thermally and optically switchable light shutters using LCs doped with push-pull azobenzene, which is known to speed up thermal relaxation. The liquid crystal light shutter can be switched between translucent and transparent states or transparent and opaque states by phase transition through changing temperature or photo-isomerization of doped azobenzene. The liquid crystal light shutter can be used for privacy windows with an initial translucent state or energy-saving windows with an initial transparent state.

Experimental vizualization of 2D photonic crystal equi-frequency contours

NASA Astrophysics Data System (ADS)

Senderakova, Dagmar; Drzik, Milan; Pisarcik, Matej

2017-12-01

Photonic crystals have been extensively studied for their unique optical properties that promise interesting novel devices. Our contribution is focused on a 2D photonic crystal structure formed by Al2O3 layer on silicon substrate, patterned with periodic hexagonal lattice of deep air holes. Azimuthal angle dependences of the specular light reflection were recorded photo-electrically at various angles of icidence and wavelengths. Data obtained were processed via mapping in reciprocal k-space. The method promises a possibility to visualize the equi-frequency contours and get more detailed information about the properties of the sample used.

Optimization of planar self-collimating photonic crystals.

PubMed

Rumpf, Raymond C; Pazos, Javier J

2013-07-01

Self-collimation in photonic crystals has received a lot of attention in the literature, partly due to recent interest in silicon photonics, yet no performance metrics have been proposed. This paper proposes a figure of merit (FOM) for self-collimation and outlines a methodical approach for calculating it. Performance metrics include bandwidth, angular acceptance, strength, and an overall FOM. Two key contributions of this work include the performance metrics and identifying that the optimum frequency for self-collimation is not at the inflection point. The FOM is used to optimize a planar photonic crystal composed of a square array of cylinders. Conclusions are drawn about how the refractive indices and fill fraction of the lattice impact each of the performance metrics. The optimization is demonstrated by simulating two spatially variant self-collimating photonic crystals, where one has a high FOM and the other has a low FOM. This work gives optical designers tremendous insight into how to design and optimize robust self-collimating photonic crystals, which promises many applications in silicon photonics and integrated optics.

Synthesis, crystal structure and magnetic properties of superconducting single crystals of HgBa2CuO4+δ

NASA Astrophysics Data System (ADS)

Bertinotti, A.; Viallet, V.; Colson, D.; Marucco, J.-F.; Hammann, J.; Forget, A.; Le Bras, G.

1996-02-01

Single crystals of HgBa2CuO4+δ of submillimetric sizes were grown with the same one step, low pressure, gold amalgamation technique used to obtain single crystals of HgBa2Ca2Cu3O8+δ. Remarkable superconducting properties are displayed by the samples which are optimally doped as grown. The sharpness of the transition profiles of the magnetic susceptibility, its anisotropy dependence and the volume fraction exhibiting the Meissner effect exceed the values obtained with the best crystal samples of Hg-1223. X-rays show that no substitutional defects have been found in the mercury plane, in particular no mixed occupancy of copper at the mercury site. The interstitial oxygen content at (1/2, 1/2, 0) δ = 0.066+/-0.008 is about one third that observed in optimally doped Hg-1223, resulting in an identical doping level per CuO2 plane in both compounds.

The effect of thermal history on crystalline structure and mechanical properties of β-nucleated isotactic polypropylene

NASA Astrophysics Data System (ADS)

Tian, Yefei; Zhou, Jian; Feng, Jiachun

2018-04-01

The effect of thermal history on β-nucleated iPP was systematically investigated by comparing the variance of crystalline microstructures and mechanical property of stepwise crystallized sample and annealed sample, which experienced different thermal history. The mechanical property tests exhibit that that the toughness of stepwise crystallized sample and annealed sample were both decreased compared to control sample, while the tensile strength of the stepwise crystallized sample increased slightly. Structure investigation showed that the α-relaxation peak, which is related to the assignment of chains in rigid amorphous phase, moved to the high temperature region for stepwise crystallized sample, while it moved to the low temperature region for annealed sample. The results indicated the weakening in rigid amorphous fraction (RAF) and the increase in lamellar thickness of β-iPP after stepwise crystallization treatment. For annealed sample, the RAF strengthened and lamellar thickness decreased slightly after thermal treatment. A mechanism of crystalline microstructures evolution of restricted area between the main lamellar under different treatments was proposed.

Crystallization kinetics of cocoa butter in the presence of sorbitan esters.

PubMed

Sonwai, Sopark; Podchong, Pawitchaya; Rousseau, Dérick

2017-01-01

Cocoa butter crystallization in the presence of sorbitan mono- and triesters or canola oil was investigated. Solid-state surfactant esters accelerated early-stage cocoa butter solidification while suppressing later growth. Sorbitan tristearate showed the strongest effect, followed by sorbitan monostearate and sorbitan monopalmitate. Liquid-state surfactants suppressed cocoa butter crystallization at all time points, with sorbitan trioleate showing a stronger effect than sorbitan monooleate, which behaved in a similar fashion to canola oil. Via DSC, the palmitic and stearic-based surfactants only associated with cocoa butter's high-melting fraction, with the oleic acid-based surfactants and canola oil showing little influence. All sorbitan esters had little effect on polymorphism, whereas canola oil accelerated the form II-to-III-to-IV transition. The palmitic and stearic-based surfactants greatly reduced cocoa butter crystal size whereas the oleic acid-based surfactants and canola showed no notable effect. Overall, sorbitan esters impacted cocoa butter crystallization kinetics, though this depended on surfactant structure and concentration. Copyright © 2016 Elsevier Ltd. All rights reserved.

Crystallization, X-ray diffraction analysis and preliminary structure determination of the polygalacturonase PehA from Agrobacterium vitis

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

Vordtriede, Paul B.; Yoder, Marilyn D., E-mail: yoderm@umkc.edu

2008-07-01

The acidic polygalacturonase PehA from A. vitis has been crystallized. A molecular-replacement solution indicated a right-handed parallel β-helix fold. Polygalacturonases are pectate-degrading enzymes that belong to glycoside hydrolase family 28 and hydrolyze the α-1,4 glycosidic bond between neighboring galacturonasyl residues of the homogalacturonan substrate. The acidic polygalacturonase PehA from Agrobacterium vitis was overexpressed in Escherichia coli, where it accumulated in the periplasmic fraction. It was purified to homogeneity via a two-step chromatography procedure and crystallized using the hanging-drop vapour-diffusion technique. PehA crystals belonged to space group P2{sub 1}, with unit-cell parameters a = 52.387, b = 62.738, c = 149.165more » Å, β = 89.98°. Crystals diffracted to 1.59 Å resolution and contained two molecules per asymmetric unit. An initial structure determination by molecular replacement indicated a right-handed parallel β-helix fold.« less

In-situ wavelength calibration and temperature control for the C-Mod high-resolution x-ray crystal imaging spectrometer

NASA Astrophysics Data System (ADS)

Delgado-Aparicio, Luis F.; Podpaly, Y.; Reinke, M. L.; Gao, C.; Rice, J.; Scott, S.; Bitter, M.; Hill, K.; Beiersdorfer, P.; Johnson, D.; Wilson, J. R.

2010-11-01

An x-ray crystal imaging spectrometer with high spectral and spatial resolution is currently being used on Alcator C-Mod to infer time histories of temperature and velocity profiles. An in-situ wavelength calibration using a 1 μm palladium filter in between the crystal and the detectors of choice is being proposed as a natural wavelength-marker using the transmission changes across the L-II and L-III edges at 3722.9 mA and 3907.1 mA, respectively. Recent results also indicate that the crystal temperature should be kept constant within a fraction of a degree since the thermal expansion of the quartz crystal will change the interplanar (2d) spacing and introduce fictitious velocity measurements of several km/s. A detailed temperature scan indicates a thermal expansion coefficient (α) of 13.5x10-6 /^oC and thus a false Doppler shift of 4.05.δT[^oC] km/s.

Design and fabrication of PZN-7%PT single crystal high frequency angled needle ultrasound transducers.

PubMed

Zhou, Qifa; Wu, Dawei; Jin, Jing; Hu, Chang-hong; Xu, Xiaochen; Williams, Jay; Cannata, Jonathan M; Lim, Leongchew; Shung, K Kirk

2008-01-01

A high-frequency angled needle ultrasound transducer with an aperture size of 0.4 x 0.56 mm2 was fabricated using a lead zinc niobate-lead titanate (PZN- 7%PT) single crystal as the active piezoelectric material. The single crystal was bonded to a conductive silver particle matching layer and a conductive epoxy backing material through direct contact curing. A parylene outer matching layer was formed by vapor deposition. Angled needle probe configuration was achieved by dicing at 45 degrees to the single crystal poling direction to satisfy a clinical request for blood flow measurement in the posterior portion of the eye. The electrical impedance magnitude and phase of the transducer were 42 Omega and -63 degrees , respectively. The measured center frequency and the fractional bandwidth at -6 dB were 43 MHz and 45%, respectively. The two-way insertion loss was approximately 17 dB. Wire phantom imaging using fabricated PZN-7%PT single crystal transducers was obtained and spatial resolutions were assessed.

Reflectance properties of one-dimensional metal-dielectric ternary photonic crystal

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

Pandey, G. N., E-mail: gnpandey2009@gmail.com; Kumar, Narendra; Thapa, Khem B.

2016-05-06

Metallic photonic crystal has a very important application in absorption enhancement in solar cells. It has been found that an ultra-thin metallic layer becomes transparent due to internal scattering of light through the each interface of the dielectric and metal surfaces. The metal has absorption due to their surface plasmon and the plasmon has important parameters for changing optical properties of the metal. We consider ternary metallic-dielectric photonic crystal (MDPC) for having large probabilities to change the optical properties of the MDPC and the photonic crystals may be changed by changing dimensionality, symmetry, lattice parameters, Filling fraction and effective refractivemore » index refractive index contrast. In this present communication, we try to show that the photonic band gap in ternary metal-dielectric photonic crystal can be significantly enlarged when air dielectric constant is considered. All the theoretical analyses are made based on the transfer matrix method together with the Drude model of metal.« less

Powder diffraction and crystal structure prediction identify four new coumarin polymorphs

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

Shtukenberg, Alexander G.; Zhu, Qiang; Carter, Damien J.

Coumarin, a simple, commodity chemical isolated from beans in 1820, has, to date, only yielded one solid state structure. Here, we report a rich polymorphism of coumarin grown from the melt. Four new metastable forms were identified and their crystal structures were solved using a combination of computational crystal structure prediction algorithms and X-ray powder diffraction. With five crystal structures, coumarin has become one of the few rigid molecules showing extensive polymorphism at ambient conditions. We demonstrate the crucial role of advanced electronic structure calculations including many-body dispersion effects for accurate ranking of the stability of coumarin polymorphs and themore » need to account for anharmonic vibrational contributions to their free energy. As such, coumarin is a model system for studying weak intermolecular interactions, crystallization mechanisms, and kinetic effects.« less

Powder diffraction and crystal structure prediction identify four new coumarin polymorphs

DOE PAGES

Shtukenberg, Alexander G.; Zhu, Qiang; Carter, Damien J.; ...

2017-05-15

Coumarin, a simple, commodity chemical isolated from beans in 1820, has, to date, only yielded one solid state structure. Here, we report a rich polymorphism of coumarin grown from the melt. Four new metastable forms were identified and their crystal structures were solved using a combination of computational crystal structure prediction algorithms and X-ray powder diffraction. With five crystal structures, coumarin has become one of the few rigid molecules showing extensive polymorphism at ambient conditions. We demonstrate the crucial role of advanced electronic structure calculations including many-body dispersion effects for accurate ranking of the stability of coumarin polymorphs and themore » need to account for anharmonic vibrational contributions to their free energy. As such, coumarin is a model system for studying weak intermolecular interactions, crystallization mechanisms, and kinetic effects.« less

Dislocation dynamics in hexagonal close-packed crystals

DOE PAGES

Aubry, S.; Rhee, M.; Hommes, G.; ...

2016-04-14

Extensions of the dislocation dynamics methodology necessary to enable accurate simulations of crystal plasticity in hexagonal close-packed (HCP) metals are presented. They concern the introduction of dislocation motion in HCP crystals through linear and non-linear mobility laws, as well as the treatment of composite dislocation physics. Formation, stability and dissociation of and other dislocations with large Burgers vectors defined as composite dislocations are examined and a new topological operation is proposed to enable their dissociation. Furthermore, the results of our simulations suggest that composite dislocations are omnipresent and may play important roles both in specific dislocation mechanisms and in bulkmore » crystal plasticity in HCP materials. While fully microscopic, our bulk DD simulations provide wealth of data that can be used to develop and parameterize constitutive models of crystal plasticity at the mesoscale.« less

Simulation of orientational coherent effects via Geant4

NASA Astrophysics Data System (ADS)

Bagli, E.; Asai, M.; Brandt, D.; Dotti, A.; Guidi, V.; Verderi, M.; Wright, D.

2017-10-01

Simulation of orientational coherent effects via Geant4 beam manipulation of high-and very-high-energy particle beams is a hot topic in accelerator physics. Coherent effects of ultra-relativistic particles in bent crystals allow the steering of particle trajectories thanks to the strong electrical field generated between atomic planes. Recently, a collimation experiment with bent crystals was carried out at the CERN-LHC, paving the way to the usage of such technology in current and future accelerators. Geant4 is a widely used object-oriented tool-kit for the Monte Carlo simulation of the interaction of particles with matter in high-energy physics. Moreover, its areas of application include also nuclear and accelerator physics, as well as studies in medical and space science. We present the first Geant4 extension for the simulation of orientational effects in straight and bent crystals for high energy charged particles. The model allows the manipulation of particle trajectories by means of straight and bent crystals and the scaling of the cross sections of hadronic and electromagnetic processes for channeled particles. Based on such a model, an extension of the Geant4 toolkit has been developed. The code and the model have been validated by comparison with published experimental data regarding the deflection efficiency via channeling and the variation of the rate of inelastic nuclear interactions.

Particle engineering using sonocrystallization: salbutamol sulphate for pulmonary delivery.

PubMed

Dhumal, Ravindra S; Biradar, Shailesh V; Paradkar, Anant R; York, Peter

2009-02-23

The aim of present work was to produce fine elongated crystals of salbutamol sulphate (SS) by sonocrystallization for pulmonary delivery and compare with micronized and spray dried SS (SDSS) for in vitro aerosolization behavior. Application of ultrasound during anti-solvent crystallization resulted in fine elongated crystals (sonocrystallized SS; SCSS) compared to aggregates of large irregular crystals obtained without sonication. Higher sonication amplitude, time, concentration and lower processing temperatures favored formation of smaller crystals with narrow particle size distribution (PSD). SCSS was separated from dispersion by spray drying in the form of loose aggregates (SD-SCSS). The fine particle fraction (FPF) of formulations with coarse lactose carrier in cascade impactor increased from 16.66% for micronized SS to 31.12% for SDSS (obtained by spray drying aqueous SS solution) and 44.21% for SD-SCSS, due to reduced cohesive/adhesive forces and aerodynamic size by virtue of elongated shape of crystals. SD-SCSS was stable without any change in crystallinity and aerodynamic behavior for 3 months at 40 degrees C/75% RH, but amorphous SDSS showed recrystallization with poor aerosolization performance on storage. Sonocrystallization, a rapid and simple technique is reported for production of SS crystals suitable for inhalation delivery.

Effects of thermal expansion of the crystal lattice on x-ray crystal spectrometers used for fusion research

NASA Astrophysics Data System (ADS)

Delgado-Aparicio, L.; Bitter, M.; Podpaly, Y.; Rice, J.; Burke, W.; Sanchez del Rio, M.; Beiersdorfer, P.; Bell, R.; Feder, R.; Gao, C.; Hill, K.; Johnson, D.; Lee, S. G.; Marmar, E.; Pablant, N.; Reinke, M. L.; Scott, S.; Wilson, R.

2013-12-01

X-ray imaging crystal spectrometers with high spectral and spatial resolution are currently being used on magnetically confined fusion devices to infer the time history profiles of ion and electron temperatures as well as plasma flow velocities. The absolute measurement of flow velocities is important for optimizing various discharge scenarios and evaluating the radial electric field in tokamak and stellarator plasmas. Recent studies indicate that the crystal temperature must be kept constant to within a fraction of a degree to avoid changes of the interplanar 2d-spacing by thermal expansion that cause changes in the Bragg angle, which could be misinterpreted as Doppler shifts. For the instrumental parameters of the x-ray crystal spectrometer on Alcator C-Mod, where those thermal effects were investigated, a change of the crystal temperature by 1 °C causes a change of the lattice spacing of the order of Δd = 1 × 10-5 Å introducing a fictitious velocity drift of the order of ˜3 km s-1. This effect must be considered for x-ray imaging crystals spectrometers installed on LHD, KSTAR, EAST, J-TEXT, NSTX and, in the future, W7-X and ITER.

Dynamics of Metamorphic Core Complexes Inferred From Modeling and Metamorphic Petrology

NASA Astrophysics Data System (ADS)

Whitney, D. L.; Rey, P.; Teyssier, C.

2008-12-01

Orogenic collapse involves extension and thinning of thick, hot, and in some cases partially molten, crust, leading to the formation of metamorphic core complexes (MCC) that are commonly cored by migmatite domes. 2D numerical modeling predicts that the geometry and P-T-t history of MCC varies as a function of the presence/absence of a partially molten layer in the deep crust; the nature of heterogeneities that localize the MCC (e.g. normal fault in upper crust vs. point-like anomaly in the deep crust); and extensional strain rate. The presence of melt in particular has a significant effect on the thermal and structural history of MCC because the presence of partially molten crust or magma bodies at depth enhances upward advection of material and heat. At high extension rate (cm/year in the region of the MCC), partially molten crust crystallizes as migmatite and cools along a high geothermal gradient (35-65 C/km); material remains partially molten during ascent, forming a migmatite dome when it crystallizes at shallower crustal levels (e.g. cordierite/sillimanite stability field). At low strain rate (mm/yr in the MCC region), the partially molten crust crystallizes at high pressure (e.g. kyanite zone); this material is subsequently deformed in the solid-state along a cooler geothermal gradient (20-35 C/km) during ascent. MCC that develop during extension of partially molten crust may therefore record distinct crystallization versus exhumation histories as a function of extensional strain rate. The mineral assemblages, metamorphic reaction histories, and structures of migmatite-cored (Mc) MCC can therefore be used to interpret the dynamics of MCC formation, e.g. "fast" McMCC in the northern N American Cordillera and Aegean regions.

Variance change point detection for fractional Brownian motion based on the likelihood ratio test

NASA Astrophysics Data System (ADS)

Kucharczyk, Daniel; Wyłomańska, Agnieszka; Sikora, Grzegorz

2018-01-01

Fractional Brownian motion is one of the main stochastic processes used for describing the long-range dependence phenomenon for self-similar processes. It appears that for many real time series, characteristics of the data change significantly over time. Such behaviour one can observe in many applications, including physical and biological experiments. In this paper, we present a new technique for the critical change point detection for cases where the data under consideration are driven by fractional Brownian motion with a time-changed diffusion coefficient. The proposed methodology is based on the likelihood ratio approach and represents an extension of a similar methodology used for Brownian motion, the process with independent increments. Here, we also propose a statistical test for testing the significance of the estimated critical point. In addition to that, an extensive simulation study is provided to test the performance of the proposed method.

Spontaneous PT symmetry breaking in Dirac-Kronig-Penney crystals

NASA Astrophysics Data System (ADS)

Longhi, Stefano; Cannata, Francesco; Ventura, Alberto

2011-12-01

We introduce a non-Hermitian PT invariant extension of the Dirac-Kronig-Penney model, describing the motion of a Dirac quasiparticle in a locally periodic sequence of imaginary δ-Dirac barriers and wells, and propose its optical realization using superstructure fiber Bragg gratings with alternating regions of optical gain and absorption. For the infinite crystal, we determine the band structure and show that the PT phase is always broken. For a finite crystal, we derive analytical expressions for reflection and transmission probabilities, and show that the PT phase is unbroken below a finite threshold of the δ-barrier area. In the proposed optical realization, the onset of PT symmetry breaking in the finite crystal corresponds to the lasing condition for the grating superstructures.

New Operational Matrices for Solving Fractional Differential Equations on the Half-Line

PubMed Central

2015-01-01

In this paper, the fractional-order generalized Laguerre operational matrices (FGLOM) of fractional derivatives and fractional integration are derived. These operational matrices are used together with spectral tau method for solving linear fractional differential equations (FDEs) of order ν (0 < ν < 1) on the half line. An upper bound of the absolute errors is obtained for the approximate and exact solutions. Fractional-order generalized Laguerre pseudo-spectral approximation is investigated for solving nonlinear initial value problem of fractional order ν. The extension of the fractional-order generalized Laguerre pseudo-spectral method is given to solve systems of FDEs. We present the advantages of using the spectral schemes based on fractional-order generalized Laguerre functions and compare them with other methods. Several numerical examples are implemented for FDEs and systems of FDEs including linear and nonlinear terms. We demonstrate the high accuracy and the efficiency of the proposed techniques. PMID:25996369

New operational matrices for solving fractional differential equations on the half-line.

PubMed

Bhrawy, Ali H; Taha, Taha M; Alzahrani, Ebraheem O; Alzahrani, Ebrahim O; Baleanu, Dumitru; Alzahrani, Abdulrahim A

2015-01-01

In this paper, the fractional-order generalized Laguerre operational matrices (FGLOM) of fractional derivatives and fractional integration are derived. These operational matrices are used together with spectral tau method for solving linear fractional differential equations (FDEs) of order ν (0 < ν < 1) on the half line. An upper bound of the absolute errors is obtained for the approximate and exact solutions. Fractional-order generalized Laguerre pseudo-spectral approximation is investigated for solving nonlinear initial value problem of fractional order ν. The extension of the fractional-order generalized Laguerre pseudo-spectral method is given to solve systems of FDEs. We present the advantages of using the spectral schemes based on fractional-order generalized Laguerre functions and compare them with other methods. Several numerical examples are implemented for FDEs and systems of FDEs including linear and nonlinear terms. We demonstrate the high accuracy and the efficiency of the proposed techniques.

Pretreatment and fractionation of wheat straw for production of fuel ethanol and value-added co-products in a biorefinery

USDA-ARS?s Scientific Manuscript database

An integrated process has been developed for a wheat straw biorefinery. In this process wheat straw was pretreated by soaking in aqueous ammonia (SAA), which extensively removed lignin but preserved high percentages of the carbohydrate fractions for subsequent bioconversion. The pretreatment condi...

Mineralogy and petrology of cretaceous subsurface lamproite sills, southeastern Kansas, USA

USGS Publications Warehouse

Cullers, R.L.; Dorais, M.J.; Berendsen, P.; Chaudhuri, Sambhudas

1996-01-01

Cores and cuttings of lamproite sills and host sedimentary country rocks in southeastern Kansas from up to 312 m depth were analyzed for major elements in whole rocks and minerals, certain trace elements in whole rocks (including the REE) and Sr isotopic composition of the whole rocks. The lamproites are ultrapotassic (K2O/Na2O = 2.0-19.9), alkalic [molecular (K2O/Na2O)/Al2O3 = 1.3-2.8], enriched in mantle-incompatible elements (light REE, Ba, Rb, Sr, Th, Hf, Ta) and have nearly homogeneous initial Sr isotopic compositions (0.707764-0.708114). These lamproites could have formed by variable degrees of partial melting of harzburgite country rock and cross-cutting veins composed of phlogopite, K-Ti richterite, titanite, diopside, K-Ti silicates, or K-Ba-phosphate under high H2O/CO2 ratios and reducing conditions. Variability in melting of veins and wall rock and variable composition of the metasomatized veins could explain the significantly different composition of the Kansas lamproites. Least squares fractionation models preclude the derivation of the Kansas lamproites by fractional crystallization from magmas similar in composition to higher silica phlogopite-sanidine lamproites some believe to be primary lamproite melts found elsewhere. In all but one case, least squares fractionation models also preclude the derivation of magmas similar in composition to any of the Kansas lamproites from one another. A magma similar in composition to the average composition of the higher SiO2 Ecco Ranch lamproite (237.5-247.5 m depth) could, however, have marginally crystallized about 12% richterite, 12% sanidine, 7% diopside and 6% phlogopite to produce the average composition of the Guess lamproite (305-312 m depth). Lamproite from the Ecco Ranch core is internally fractionated in K2O, Al2O3, Ba, MgO, Fe2O3, Co and Cr most likely by crystal accumulation-removal of ferromagnesian minerals and sanidine. In contrast, the Guess core (305-312 m depth) has little fractionation throughout most of the sill except in several narrow zones. Lamproite in the Guess core has large enrichments in TiO2, Ba, REE, Th, Ta and Sc and depletions in MgO, Cr, Co and Rb possibly concentrated in these narrow zones during the last dregs of crystallization of this magma. The Ecco Ranch sill did not show any evidence of loss of volatiles or soluble elements into the country rock. This contrasts to the previously studied, shallow Silver City lamproite which did apparently lose H2O-rich fluid to the country rock. Perhaps a greater confining pressure and lesser amount of H2O-rich fluid prevented it from escaping.

Experimental Investigation of Turbulence-Chemistry Interaction in High-Reynolds-Number Turbulent Partially Premixed Flames

DTIC Science & Technology

2016-06-23

4 . TITLE AND SUBTITLE [U] Experimental investigation of turbulence-chemistry interaction in high-Reynolds-number 5a. CONTRACT NUMBER turbulent...nonpremixed/partially premixed flames and turbulence-chemistry interaction. Turbulent mixing of mixture fraction has been studied extensively [ 4 , 14]. In a...two-feed non-premixed flame, the mixture fraction is defined as: ξ = Y − Yo YF − Yo (1) where Y is a conserved quantity such as the mass fraction of any

Failures of fractional crystallization: ordered co-crystals of isomers and near isomers.

PubMed

Kelley, Steven P; Fábián, László; Brock, Carolyn Pratt

2011-02-01

A list of 270 structures of ordered co-crystals of isomers, near isomers and molecules that are almost the same has been compiled. Searches for structures containing isomers could be automated by the use of IUPAC International Chemical Identifier (InChI™) strings but searches for co-crystals of very similar molecules were more labor intensive. Compounds in which the heteromolecular A···B interactions are clearly better than the average of the homomolecular A···A and B···B interactions were excluded. The two largest structural classes found include co-crystals of configurational diastereomers and of quasienantiomers (or quasiracemates). These two groups overlap. There are 114 co-crystals of diastereomers and the same number of quasiracemates, with 71 structures being counted in both groups; together the groups account for 157 structures or 58% of the total. The large number of quasiracemates is strong evidence for inversion symmetry being very favorable for crystal packing. Co-crystallization of two diastereomers is especially likely if a 1,1 switch of a methyl group and an H atom, or of an inversion of a [2.2.1] or [2.2.2] cage, in one of the diastereomers would make the two molecules enantiomers.

Kinetics of the current response in TlBr detectors under a high dose rate of {gamma}-ray irradiation

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

Gazizov, I. M., E-mail: gazizov@isotop.dubna.ru; Zaletin, V. M.; Kukushkin, V. M.

2012-03-15

The kinetics of the photocurrent response in doped and undoped TlBr samples subjected to irradiation with {gamma}-ray photons from a {sup 137}Cs source with the dose rate 0.033 to 3.84 Gy/min are studied. The crystals were grown by the directional crystallization of the melt method using the Bridgman-Stockbarger technique. The Pb impurity mass fraction introduced into the doped TlBr crystals was 1-10 ppm and amounted to 150 ppm for the Ca impurity. The crystals were grown in a vacuum, in bromine vapors, in a hydrogen atmosphere, and in air. Decay of the photocurrent is observed for extrinsic semiconductor crystals dopedmore » with bivalent cations (irrespective of the growth atmosphere), and also for crystals grown in hydrogen and crystals grown in an excess of thallium. The time constant of photocurrent decay {tau} amounted to 30-1400 s and was proportional to resistivity. It is shown that the current response can be related to photolysis in the TlBr crystals during irradiation with {gamma}-ray photons. The energy of hole traps responsible for a slow increase in the photo-current has been estimated and found to be equal to 0.6-0.85 eV.« less

Complete stress-induced depolarization of relaxor ferroelectric crystals without transition through a non-polar phase

NASA Astrophysics Data System (ADS)

Shkuratov, Sergey I.; Baird, Jason; Antipov, Vladimir G.; Hackenberger, Wesley; Luo, Jun; Zhang, Shujun; Lynch, Christopher S.; Chase, Jay B.; Jo, Hwan R.; Roberts, Christopher C.

2018-03-01

The development of relaxor ferroelectric single crystal technology is driven by the ability to tailor ferroelectric properties through domain engineering not achievable in polycrystalline materials. In this study, three types of domain-engineered rhombohedral Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 crystals were subjected to transverse high strain rate loading. The experimental results indicate that the domain configuration has a significant effect on the stress-induced depolarization and the associated charge released. A complete depolarization of the single-domain crystals with 3m symmetry is observed, while multidomain crystals with 4mm and mm2 symmetries retain a fraction of their initial remanent polarization. The complete depolarization of single-domain crystals is unique without transition to a non-polar phase, with a stress-induced charge density of 0.48 C/m2. This is up to three times higher than that of the multidomain crystals and PbZrxTi1-xO3 ferroelectric ceramics that are critical for ultrahigh-power transducer applications. The main offering of this work is to propose a detailed mechanism for complete stress-induced depolarization in ferroelectric crystals which does not involve an intermediate transformation to a non-polar phase.

Self-organized chiral colloidal crystals of Brownian square crosses.

PubMed

Zhao, Kun; Mason, Thomas G

2014-04-16

We study aqueous Brownian dispersions of microscale, hard, monodisperse platelets, shaped as achiral square crosses, in two dimensions (2D). When slowly concentrated while experiencing thermal excitations, the crosses self-organize into fluctuating 2D colloidal crystals. As the particle area fraction φA is raised, an achiral rhombic crystal phase forms at φA ≈ 0.52. Above φA ≈ 0.56, the rhombic crystal gives way to a square crystal phase that exhibits long-range chiral symmetry breaking (CSB) via a crystal-crystal phase transition; the observed chirality in a particular square crystallite has either a positive or a negative enantiomeric sense. By contrast to triangles and rhombs, which exhibit weak CSB as a result of total entropy maximization, square crosses display robust long-range CSB that is primarily dictated by how they tile space at high densities. We measure the thermal distribution of orientation angles γ of the crosses' arms relative to the diagonal bisector of the local square crystal lattice as a function of φA, and the average measured γ (φA) agrees with a re-scaled model involving efficient packing of rotated cross shapes. Our findings imply that a variety of hard achiral shapes can be designed to form equilibrium chiral phases by considering their tiling at high densities.

Understanding the rheology of two and three-phase magmas

NASA Astrophysics Data System (ADS)

Coats, R.; Cai, B.; Kendrick, J. E.; Wallace, P. A.; Hornby, A. J.; Miwa, T.; von Aulock, F. W.; Ashworth, J. D.; Godinho, J.; Atwood, R. C.; Lee, P. D.; Lavallée, Y.

2017-12-01

The rheology of magma plays a fundamental role in determining the style of a volcanic eruption, be it explosive or effusive. Understanding how magmas respond to changes in stress/ strain conditions may help to enhance eruption forecast models. The presence of crystals and bubbles in magmas alter the viscosity of suspensions and favor a non-Newtonian response. Thus, with the aim of grasping the rheological behavior of volcanic materials, uniaxial compressive tests were performed on natural and synthetic samples. A suite of variably porous (10-32 vol.%), highly crystalline ( 50 vol.%) dacite from the 1991-95 eruption of Mt Unzen, Japan, was selected as the natural material, while synthetic samples were sintered with desired porosities (<3, 20 and 30 vol.%) and TiO2 particles (0-50 vol.%). Tests were carried out at both room temperature and above the glass transition temperature (Tg) of the different materials to cover the entirety of the extrusion process. Room temperature tests were performed at constant strain rates of 10-1, 10-3, and 10-5 s-1. The response was brittle and peak stresses reached were positively correlated to strain rate and negatively correlated to porosity. At temperatures above Tg, strain rates of 10-3, 10-4, and 10-5 s-1 were imposed resulting in dominantly brittle, transitional and dominantly viscous responses, respectively. Samples with a brittle response reached higher peak stresses, and strain-to-failure values, at high temperature than at room temperature. In both materials, non-Newtonian, shear-thinning behavior was observed and while synthetic samples showed an expected increase in apparent viscosity with increasing crystal content, surprisingly natural samples did not show a correlation between apparent viscosity and porosity. We hypothesise this is due to crystal content being the governing factor for the volume fractions explored. In situ, high temperature synchrotron X-ray tomography was performed on selected crystal/pore volume fractions at Diamond Light Source. Unexpectedly, these observations suggest that fractures nucleate in crystals due to crystal interactions, before propagating through the interstitial melt. This ongoing study promises to uncover the way crystal-bearing magmas flow or fail, necessary to constrain magmatic processes and volcanic hazards.