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.

Influence of crude oil cracking on distribution of hydrocarbons in the Earth's interior (experimental data)

NASA Astrophysics Data System (ADS)

Balitsky, V. S.; Balitskaya, L. V.; Penteley, S. V.; Novikova, M. A.

2012-02-01

The compositions and phase conditions of water-hydrocarbon fluids in synthetic quartz inclusions were studied by the methods of microthermometry, local IR spectroscopy, and gas-liquid chromatography. Synthetic quartz was grown in near-neutral fluoride, low-alkali bicarbonate, and alkali carbonate solutions with crude oil and its major fractions. The crystals with fluid inclusions were grown under thermal gradient conditions at relatively low temperatures (240-280°C) and pressures (6-45 MPa). After the study, the inclusions of grown crystals were subject to thermal processing in autoclaves at 350-380°C and 80-125 MPa. As a result, the initial water-hydrocarbon inclusions underwent significant changes. Hydrocarbon gases, largely methane and residual solid bitumens, appeared in their composition; the gasoline-kerosene fraction content increased substantially in liquid hydrocarbons (HCs). These changes are caused, first of all, by crude oil cracking, which is manifested already at 330°C and attains its maximum activity at 350-500°C (pressure of saturated vapor and higher). In natural conditions with increase in depths and, thus, the thermobaric parameters, this process is inevitable. According to the obtained experimental data, this very phenomenon and the existence of real thermal and baric gradients in the Earth's interior provide for the formation of vertical zoning in the distribution of hydrocarbon deposits of different types.

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.

Petrogenesis of the Northwest Africa 4898 high-Al mare basalt

NASA Astrophysics Data System (ADS)

Li, Shaolin; Hsu, Weibiao; Guan, Yunbin; Wang, Linyan; Wang, Ying

2016-07-01

Northwest Africa (NWA) 4898 is the only low-Ti, high-Al basaltic lunar meteorite yet recognized. It predominantly consists of pyroxene (53.8 vol%) and plagioclase (38.6 vol%). Pyroxene has a wide range of compositions (En12-62Fs25-62Wo11-36), which display a continuous trend from Mg-rich cores toward Ca-rich mantles and then to Fe-rich rims. Plagioclase has relatively restricted compositions (An87-96Or0-1Ab4-13), and was transformed to maskelynite. The REE zoning of all silicate minerals was not significantly modified by shock metamorphism and weathering. Relatively large (up to 1 mm) olivine phenocrysts have homogenous inner parts with Fo ~74 and sharply decrease to 64 within the thin out rims (~30 μm in width). Four types of inclusions with a variety of textures and modal mineralogy were identified in olivine phenocrysts. The contrasting morphologies of these inclusions and the chemical zoning of olivine phenocrysts suggest NWA 4898 underwent at least two stages of crystallization. The aluminous chromite in NWA 4898 reveals that its high alumina character was inherited from the parental magma, rather than by fractional crystallization. The mineral chemistry and major element compositions of NWA 4898 are different from those of 12038 and Luna 16 basalts, but resemble those of Apollo 14 high-Al basalts. However, the trace element compositions demonstrate that NWA 4898 and Apollo 14 high-Al basalts could not have been derived from the same mantle source. REE compositions of its parental magma indicate that NWA 4898 probably originated from a unique depleted mantle source that has not been sampled yet. Unlike Apollo 14 high-Al basalts, which assimilated KREEPy materials during their formation, NWA 4898 could have formed by closed-system fractional crystallization.

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.

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.

Defect-induced solid state amorphization of molecular crystals

NASA Astrophysics Data System (ADS)

Lei, Lei; Carvajal, Teresa; Koslowski, Marisol

2012-04-01

We investigate the process of mechanically induced amorphization in small molecule organic crystals under extensive deformation. In this work, we develop a model that describes the amorphization of molecular crystals, in which the plastic response is calculated with a phase field dislocation dynamics theory in four materials: acetaminophen, sucrose, γ-indomethacin, and aspirin. The model is able to predict the fraction of amorphous material generated in single crystals for a given applied stress. Our results show that γ-indomethacin and sucrose demonstrate large volume fractions of amorphous material after sufficient plastic deformation, while smaller amorphous volume fractions are predicted in acetaminophen and aspirin, in agreement with experimental observation.

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.

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.

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.

Petrogenesis and origin of the Upper Jurassic-Lower Cretaceous magmatism in Central High Atlas (Morocco): Major, trace element and isotopic (Sr-Nd) constraints

NASA Astrophysics Data System (ADS)

Essaifi, Abderrahim; Zayane, Rachid

2018-01-01

During an uplift phase, which lasted ca. 40 Ma, from the Late Jurassic (165 Ma) to the Early Cretaceous (125 Ma), transitional to moderately alkaline magmatic series were emplaced in the Central High Atlas. The corresponding magmatic products include basaltic lava flows erupted within wide synclines and intrusive complexes composed of layered mafic intrusions and monzonitic to syenitic dykes emplaced along narrow anticlinal ridges. The igneous rock sequence within the intrusive complexes is composed of troctolites, olivine-gabbros, oxide-gabbros, monzonites and syenites. The chemical compositions of the various intrusive rocks can be accounted for by crystal accumulation, fractional crystallization and post-magmatic remobilization. The evolution from the troctolites to the syenites was mainly controlled by a fractional crystallization process marked by early fractionation of olivine, plagioclase and clinopyroxene, followed by separation of biotite, amphibole, apatite, and Ti-magnetite. Hydrothermal activity associated with emplacement of the intrusions within the Jurassic limestones modified the elemental and the Sr isotopic composition of the hydrothermally altered rocks In particular the monzonitic to syenitic dykes underwent an alkali metasomatism marked by depletion in K and Rb and enrichment in Na and Sr. As a result, their Sr isotopic composition was shifted towards higher initial Sr isotopic ratios (0.7067-0.7075) with respect to the associated gabbros (0.7036-0.7046). On the contrary, the Nd isotopic compositions were preserved from isotope exchange with the limestones and vary in a similar range to those of the gabbros (+1.6 < εNdi < +4.1). The isotopic and the trace element ratios of the uncontaminated samples were used to constrain the source characteristics of this magmatism. The Sr-Nd isotopic data and the incompatible element ratios (e.g. La/Nb, Zr/Nb, Th/U, Ce/Pb) are consistent with generation from an enriched upper mantle similar to an ocean island basalt source. Melting of the subcontinental metasomatized lithosphere is tentatively related to small-scale shallow mantle upwelling and asthenospheric uprise at the triple junction between the western High Atlas, the Middle Atlas and the eastern High Atlas domains during a period of relative tectonic quiescence.

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.

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.

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.

Chemical versus temporal controls on the evolution of tholeiitic and calc-alkaline magmas at two volcanoes in the Alaska-Aleutian arc

USGS Publications Warehouse

George, R.; Turner, S.; Hawkesworth, C.; Bacon, C.R.; Nye, C.; Stelling, P.; Dreher, S.

2004-01-01

The Alaska-Aleutian island arc is well known for erupting both tholeiitic and calc-alkaline magmas. To investigate the relative roles of chemical and temporal controls in generating these contrasting liquid lines of descent we have undertaken a detailed study of tholeiitic lavas from Akutan volcano in the oceanic A1eutian arc and calc-alkaline products from Aniakchak volcano on the continental A1askan Peninsula. The differences do not appear to be linked to parental magma composition. The Akutan lavas can be explained by closed-system magmatic evolution, whereas curvilinear trace element trends and a large range in 87 Sr/86 Sr isotope ratios in the Aniakchak data appear to require the combined effects of fractional crystallization, assimilation and magma mixing. Both magmatic suites preserve a similar range in 226 Ra-230 Th disequilibria, which suggests that the time scale of crustal residence of magmas beneath both these volcanoes was similar, and of the order of several thousand years. This is consistent with numerical estimates of the time scales for crystallization caused by cooling in convecting crustal magma chambers. During that time interval the tholeiitic Akutan magmas underwent restricted, closed-system, compositional evolution. In contrast, the calc-alkaline magmas beneath Aniakchak volcano underwent significant open-system compositional evolution. Combining these results with data from other studies we suggest that differentiation is faster in calc-alkaline and potassic magma series than in tholeiitic series, owing to a combination of greater extents of assimilation, magma mixing and cooling.

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].

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.

Crustal contamination and crystal entrapment during polybaric magma evolution at Mt. Somma-Vesuvius volcano, Italy: Geochemical and Sr isotope evidence

USGS Publications Warehouse

Piochi, M.; Ayuso, R.A.; de Vivo, B.; Somma, R.

2006-01-01

New major and trace element analyses and Sr-isotope determinations of rocks from Mt. Somma-Vesuvius volcano produced from 25 ky BP to 1944 AD are part of an extensive database documenting the geochemical evolution of this classic region. Volcanic rocks include silica undersaturated, potassic and ultrapotassic lavas and tephras characterized by variable mineralogy and different crystal abundance, as well as by wide ranges of trace element contents and a wide span of initial Sr-isotopic compositions. Both the degree of undersaturation in silica and the crystal content increase through time, being higher in rocks produced after the eruption at 472 AD (Pollena eruption). Compositional variations have been generally thought to reflect contributions from diverse types of mantle and crust. Magma mixing is commonly invoked as a fundamental process affecting the magmas, in addition to crystal fractionation. Our assessment of geochemical and Sr-isotopic data indicates that compositional variability also reflects the influence of crustal contamination during magma evolution during upward migration to shallow crustal levels and/or by entrapment of crystal mush generated during previous magma storage in the crust. Using a variant of the assimilation fractional crystallization model (Energy Conservation-Assimilation Fractional Crystallization; [Spera and Bohrson, 2001. Energy-constrained open-system magmatic processes I: General model and energy-constrained assimilation and fractional crystallization (EC-AFC) formulation. J. Petrol. 999-1018]; [Bohrson, W.A. and Spera, F.J., 2001. Energy-constrained open-system magmatic process II: application of energy-constrained assimilation-fractional crystallization (EC-AFC) model to magmatic systems. J. Petrol. 1019-1041]) we estimated the contributions from the crust and suggest that contamination by carbonate rocks that underlie the volcano (2 km down to 9-10 km) is a fundamental process controlling magma compositions at Mt. Somma-Vesuvius in the last 8 ky BP. Contamination in the mid- to upper crust occurred repeatedly, after the magma chamber waxed with influx of new mantle- and crustal-derived magmas and fluids, and waned as a result of magma withdrawal and production of large and energetic plinian and subplinian eruptions. ?? 2005 Elsevier B.V. All rights reserved.

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.

Pressure increases, the for­mation of chromite seams, and the development of the ultramafic series in the Stillwater Complex, Montana

USGS Publications Warehouse

Lipin, Bruce R.

1993-01-01

This paper explores the hypothesis that chromite seams in the Stillwater Complex formed in response to periodic increases in total pressure in the chamber. Total pressure increased because of the positive δV of nucleation of CO2 bubbles in the melt and their subsequent rise through the magma chamber, during which the bubbles increased in volume by a factor of 4–6. By analogy with the pressure changes in the summit chambers of Kilauea and Krafla volcanoes, the maximum variation was 0⋅2–0⋅25 kbar, or 5–10% of the total pressure in the Stillwater chamber. An evaluation of the likelihood of fountaining and mixing of a new, primitive liquid that entered the chamber with the somewhat more evolved liquid already in the chamber is based upon calculations using observed and inferred velocities and flow rates of basaltic magmas moving through volcanic fissures. The calculations indicate that hot, dense magma would have oozed, rather than fountained into the chamber, and early mixing of the new and residual magmas that could have resulted in chromite crystallizing alone did not take place.Mixing was an important process in the Stillwater magma chamber, however. After the new magma in the chamber underwent ˜5% fractional crystallization, its composition, temperature, and density approached those of the overlying liquid in the chamber and the liquids then mixed. If this process occurred many times over the course of the development of the Ultramafic series, a thick column of magma with orthopyroxene on its liquidus would have been the result. Thus, the sequence of multiple injections, fractionation, and mixing with previously fractionated magma could have been the mechanism that produced the thick bronzite cumulate layer (the Bronzitite zone) above the cyclic units.

Atmospheric outgassing and native-iron formation during carbonaceous sediment-basalt melt interactions

NASA Astrophysics Data System (ADS)

Pernet-Fisher, John F.; Day, James M. D.; Howarth, Geoffrey H.; Ryabov, Victor V.; Taylor, Lawrence A.

2017-02-01

Organic carbon-rich sediment assimilation by basaltic magmas leads to enhanced emission of greenhouse gases during continental flood basalt eruptions. A collateral effect of these interactions is the generation of low oxygen fugacities (fO2) (below the iron-wüstite [IW] buffer curve) during magmatic crystallization, resulting in the precipitation of native-iron. The occurrence of native-iron bearing terrestrial basaltic rocks are rare, having been identified at three locations: Siberia, West Greenland, and Central Germany. We report the first combined study of Re-Os isotopes, highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, Re), and trace-element abundances for these three occurrences, in addition to host sediments at West Greenland. To quantify the amount of crustal assimilation experienced by the magmas, we present combined crystallization and assimilation models, together with fractional crystallization models, to assess how relative abundances of the HSE have been modified during crystallization. The radiogenic osmium isotopic compositions (γOsinitial +15 to +193) of mafic igneous samples are consistent with assimilation of old high Re/Os crustal contaminants with radiogenic 187Os/188Os, whereas the HSE inter-element fractionations (Pd/Os 2 to >10,000) suggest that some Siberian samples underwent an early stage of sulfide removal. Metalliferous samples from the Siberian intrusions of Khungtukun and Dzhaltul (associated with the Siberian flood basalts) yield internal 187Re-187Os ages of 266 ± 83Ma and 249 ± 50Ma, respectively, reflecting late-Permian emplacement ages. These results imply that crustal assimilation took place prior to crystallization of native-Fe. In contrast, metalliferous samples from Disko Island and Bühl (associated with the West Greenland flood basalts, and the Central European Volcanic Province, respectively) have trends in 187Re/188Os-187Os/188Os space corresponding to apparent ages older than their reported crystallization ages. These anomalous ages probably reflect concurrent assimilation of high Re/Os, radiogenic 187Os crust during crystallization of native-Fe, consistent with the character of local West Greenland sediments. In all three locations, calculations of combined assimilation of crustal sediments and fractional crystallization indicate between 1-7% assimilation can account for the Os-isotope systematics. In the case of Siberian samples, incompatible trace-element abundances indicate that lower crustal assimilation may have also occurred, consistent with the suggestion that crustal assimilation took place prior to native-Fe precipitation. The extent of local crustal contamination at Siberia, West Greenland, and Bühl necessitates that significant quantities of CH4, CO, CO2, SO2 and H2 O were released during assimilation of carbonaceous sediments. Consequently, carbonaceous sediment-basalt melt interactions have collateral effects on total gas output from flood basalt volcanism into the atmosphere. However, the amount of carbonaceous sediment contamination experienced by melts forming the Khungtukun and Dzhaltul intrusions alone, cannot explain the major C-isotope excursions at the Permo-Triassic mass-extinction event. Instead, further unsampled intrusions that also experienced significant carbonaceous sediment-melt interactions would be required. Enhanced greenhouse gas-emission during the Permo-Triassic mass extinction may have been facilitated by a combination of mantle melting and carbonaceous sediment-melt interactions, together with other proposed mechanisms, including wildfires, or by microbial metabolic exhalation.

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.

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.

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.

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.

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.

Magmatic processes revealed by anorthoclase textures and trace element modeling: The case of the Lajes Ignimbrite eruption (Terceira Island, Azores)

NASA Astrophysics Data System (ADS)

D'Oriano, Claudia; Landi, Patrizia; Pimentel, Adriano; Zanon, Vittorio

2017-11-01

The Lajes Ignimbrite on Terceira Island (Azores) records the last major pyroclastic density current-forming eruption of Pico Alto Volcano that occurred ca. 21 kyrs ago. This comenditic trachyte ignimbrite contains up to 30 vol% of crystals, mostly anorthoclase. Geochemical investigation of the products collected throughout two key outcrops reveals that major element compositions are poorly variable, whereas trace elements show significant variability, pointing to the presence of a zoned magma reservoir. Thermometry and oxygen fugacity estimations yielded pre-eruptive temperatures of 850-900 °C and ΔNNO from - 2.4 to - 1.8. Melt-alkali-feldspar hygrometer indicates magmatic H2O contents ranging from 5.8 wt% in the upper part of the reservoir to 3.6 wt% at the bottom, indicating that the magma reservoir (confined at 4 km depth) was mainly water-undersaturated before the eruption, except for the topmost portion. Two types of anorthoclase crystals were identified. Type 1 crystals show reverse to oscillatory zoning with An contents of 0.4-2.1 mol% and Ba of 200-2000 ppm. They formed in the middle/upper portion of the reservoir, where fractional crystallization processes dominated. Type 2 crystals, mainly present in the less evolved products, are characterized by patchy-zoned cores with large dissolution pockets surrounded by thick oscillatory-zoned rims and show a wide compositional range (An of 0.5-4.7 mol% and Ba of 142-4824 ppm). Their zoning patterns, together with whole-rock and glass compositions of the juvenile clasts, are consistent with the involvement of an anorthoclase-bearing cumulate from the bottom of the reservoir that underwent partial melting. Crystal dissolution was likely induced by the presence of a heat source at depth, without any mass transfer to the eruptible magma, as suggested by the lack of petrographic and chemical evidences of mixing between the resident comenditic trachyte and a mafic/intermediate magma. Thermal instability generated convective plumes that were responsible for the admittance of crystals from the cumulate level into the intermediate portions of the magma reservoir and possibly acted as trigger of the explosive eruption.

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.

The formation of jupiter, the jovian early bombardment and the delivery of water to the asteroid belt: the case of (4) vesta.

PubMed

Turrini, Diego; Svetsov, Vladimir

2014-01-28

The asteroid (4) Vesta, parent body of the Howardite-Eucrite-Diogenite meteorites, is one of the first bodies that formed, mostly from volatile-depleted material, in the Solar System. The Dawn mission recently provided evidence that hydrated material was delivered to Vesta, possibly in a continuous way, over the last 4 Ga, while the study of the eucritic meteorites revealed a few samples that crystallized in presence of water and volatile elements. The formation of Jupiter and probably its migration occurred in the period when eucrites crystallized, and triggered a phase of bombardment that caused icy planetesimals to cross the asteroid belt. In this work, we study the flux of icy planetesimals on Vesta during the Jovian Early Bombardment and, using hydrodynamic simulations, the outcome of their collisions with the asteroid. We explore how the migration of the giant planet would affect the delivery of water and volatile materials to the asteroid and we discuss our results in the context of the geophysical and collisional evolution of Vesta. In particular, we argue that the observational data are best reproduced if the bulk of the impactors was represented by 1-2 km wide planetesimals and if Jupiter underwent a limited (a fraction of au) displacement.

The Formation of Jupiter, the Jovian Early Bombardment and the Delivery of Water to the Asteroid Belt: The Case of (4) Vesta

PubMed Central

Turrini, Diego; Svetsov, Vladimir

2014-01-01

The asteroid (4) Vesta, parent body of the Howardite-Eucrite-Diogenite meteorites, is one of the first bodies that formed, mostly from volatile-depleted material, in the Solar System. The Dawn mission recently provided evidence that hydrated material was delivered to Vesta, possibly in a continuous way, over the last 4 Ga, while the study of the eucritic meteorites revealed a few samples that crystallized in presence of water and volatile elements. The formation of Jupiter and probably its migration occurred in the period when eucrites crystallized, and triggered a phase of bombardment that caused icy planetesimals to cross the asteroid belt. In this work, we study the flux of icy planetesimals on Vesta during the Jovian Early Bombardment and, using hydrodynamic simulations, the outcome of their collisions with the asteroid. We explore how the migration of the giant planet would affect the delivery of water and volatile materials to the asteroid and we discuss our results in the context of the geophysical and collisional evolution of Vesta. In particular, we argue that the observational data are best reproduced if the bulk of the impactors was represented by 1–2 km wide planetesimals and if Jupiter underwent a limited (a fraction of au) displacement. PMID:25370027

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

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.

A Successful Synthesis of the CoCrFeNiAl0.3 Single-Crystal, High-Entropy Alloy by Bridgman Solidification

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

Ma, S. G.; Zhang, S. F.; Gao, M. C.

2013-08-22

For the first time, a face-centered-cubic, single-crystal CoCrFeNiAl{sub 0.3} (designated as Al0.3), high-entropy alloy (HEA) was successfully synthesized by the Bridgman solidification (BS) method, at an extremely low withdrawal velocity through a constant temperature gradient, for which it underwent two BS steps. Specially, at the first BS step, the alloy sample underwent several morphological transitions accompanying the crystal growth from the melt. This microstructure evolves from as-cast dendrites, to equiaxed grains, and then to columnar crystals, and last to the single crystal. In particular, at the equiaxed-grain region, some visible annealing twins were observed, which indicates a low stacking faultmore » energy of the Al0.3 alloy. Although a body-centered- cubic CoCrFeNiAl (Al1) HEA was also prepared under the same conditions, only a single columnar-crystal structure with instinctively preferential crystallographic orientations was obtained by the same procedure. A similar morphological transition from dendrites to equiaxed grains occurred at the equiaxed-grain region in Al1 alloy, but the annealing twins were not observed probably because a higher Al addition leads to a higher stacking fault energy for this alloy.« less

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.

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

Lower continental crust formation through focused flow in km-scale melt conduits: The zoned ultramafic bodies of the Chilas Complex in the Kohistan island arc (NW Pakistan)

NASA Astrophysics Data System (ADS)

Jagoutz, O.; Müntener, O.; Burg, J.-P.; Ulmer, P.; Jagoutz, E.

2006-02-01

Whole-rock and Sm-Nd isotopic data of the main units of the Chilas zoned ultramafic bodies (Kohistan paleo-island arc, NW Pakistan) indicate that ultramafic rocks and gabbronorite sequences stem from a common magma. However, field observations rule out formation of both ultramafic and mafic sequences in terms of gravitational crystal settling in a large magma chamber. Contacts between ultramafic and gabbronorite sequences show emplacement of the dunitic bodies into a semi-consolidated gabbronoritic crystal-mush, which in turn has intruded and reacted with the ultramafic rocks to produce concentric zoning. Field and petrological observations indicate a replacive origin of the dunite. Bulk Mg#'s of dunitic rocks range from 0.87-0.81 indicating that the dunite-forming melt underwent substantial fractionation-differentiation and that percolative fractional crystallization probably generated the dunitic core. The REE chemistry of clinopyroxene in primitive dunite samples and the Nd isotopic composition of ultramafic rocks are in equilibrium with the surrounding gabbronorite. Accordingly, liquids that formed the dunitic rocks and later the mafic sequence derived from a similar depleted source ( ɛNd˜4.8). We propose a mechanism for the comagmatic emplacement, where km-scale ultramafic bodies represent continuous channels reaching down into the upper mantle. The melt-filled porosity in these melt channels diminishes the mean-depth-integrated density difference to the surrounding rocks. Due to buoyancy forces, melt channels raise into the overlying crustal sequence. In the light of such processes, the ultramafic bodies are interpreted as melt channels through which the Chilas gabbronorite sequence was fed. The estimated basaltic-andesitic, low Mg# (˜0.53) bulk composition of the Chilas gabbronorite sequence closely matches estimates of lower crustal compositions. Since the mafic sequence originated from a primary, high Mg# (> 0.7) basaltic arc magma, differentiation of such high Mg# magmas within km-scale isolated melt conduits may explain the "Mg#-gap" between bulk estimates of the continental crust and primary basaltic magmas, a major paradox in the andesite model of crust formation.

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.

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.

The rheology of crystal-rich magmas (Kuno Award Lecture)

NASA Astrophysics Data System (ADS)

Huber, Christian; Aldin Faroughi, Salah; Degruyter, Wim

2016-04-01

The rheology of magmas controls not only eruption dynamics but also the rate of transport of magmas through the crust and to a large extent the rate of magma differentiation and degassing. Magma bodies stalled in the upper crust are known to spend most of their lifespan above the solidus at a high crystal content (Cooper and Kent, 2014; Huber et al., 2009), where the probability of melt extraction (crystal fractionation) is the greatest (Dufek and Bachmann, 2010). In this study, we explore a new theoretical framework to study the viscosity of crystal bearing magmas. Since the seminal work of A. Einstein and W. Sutherland in the early 20th century, it has been shown theoretically and tested experimentally that a simple self-similar behavior exist between the relative viscosity of dilute (low crystal content) suspensions and the particle volume fraction. The self-similar nature of that relationship is quickly lost as we consider crystal fractions beyond a few volume percent. We propose that the relative viscosity of crystal-bearing magmas can be fully described by two state variables, the intrinsic viscosity and the crowding factor (a measure of the packing threshold in the suspension). These two state variables can be measured experimentally under different conditions, which allows us to develop closure relationships in terms of the applied shear stress and the crystal shape and size distributions. We build these closure equations from the extensive literature on the rheology of synthetic suspensions, where the nature of the particle shape and size distributions is better constrained and apply the newly developed model to published experiments on crystal-bearing magmas. We find that we recover a self-similar behavior (unique rheology curve) up to the packing threshold and show that the commonly reported break in slope between the relative viscosity and crystal volume fraction around the expected packing threshold is most likely caused by a sudden change in the state of dispersion of the magma (change in the state variables caused by either shear localization or crystal breakage). We argue that the model we propose is a first step to go beyond fitting experimental data and towards building a predictive rheology model for crystal-bearing magmas. Cooper, K.M., and Kent, A.J.R. (2014) Rapid remobilization of magmatic crystals kept in cold storage. Nature, 506(7489), 480-483. Dufek, J., and Bachmann, O. (2010) Quantum magmatism: Magmatic compositional gaps generated by melt-crystal dynamics. Geology, 38(8), 687-690. Huber, C., Bachmann, O., and Manga, M. (2009) Homogenization processes in silicic magma chambers by stirring and mushification (latent heat buffering). Earth and Planetary Science Letters, 283(1-4), 38-47.

Fractional crystallization-induced variations in sulfides from the Noril’sk-Talnakh mining district (polar Siberia, Russia)

USGS Publications Warehouse

Duran, C.J.; Barnes, S-J.; Pleše, P.; Prašek, M. Kudrna; Zientek, Michael L.; Pagé, P.

2017-01-01

The distribution of platinum-group elements (PGE) within zoned magmatic ore bodies has been extensively studied and appears to be controlled by the partitioning behavior of the PGE during fractional crystallization of magmatic sulfide liquids. However, other chalcophile elements, especially TABS (Te, As, Bi, Sb, and Sn) have been neglected despite their critical role in forming platinum-group minerals (PGM). TABS are volatile trace elements that are considered to be mobile so investigating their primary distribution may be challenging in magmatic ore bodies that have been somewhat altered. Magmatic sulfide ore bodies from the Noril’sk-Talnakh mining district (polar Siberia, Russia) offer an exceptional opportunity to investigate the behavior of TABS during fractional crystallization of sulfide liquids and PGM formation as the primary features of the ore bodies have been relatively well preserved. In this study, new petrographic (2D and 3D) and whole-rock geochemical data from Cu-poor to Cu-rich sulfide ores of the Noril’sk-Talnakh mining district are integrated with published data to consider the role of fractional crystallization in generating mineralogical and geochemical variations across the different ore types (disseminated to massive). Despite textural variations in Cu-rich massive sulfides (lenses, veins, and breccias), these sulfides have similar chemical compositions, which suggests that Cu-rich veins and breccias formed from fractionated sulfide liquids that were injected into the surrounding rocks. Numerical modeling using the median disseminated sulfide composition as the initial sulfide liquid composition and recent DMSS/liq and DISS/liq predicts the compositional variations observed in the massive sulfides, especially in terms of Pt, Pd, and TABS. Therefore, distribution of these elements in the massive sulfides was likely controlled by their partitioning behavior during sulfide liquid fractional crystallization, prior to PGM formation. Our observations indicate that in the Cu-poor massive sulfides the PGM formed as the result of exsolution from sulfide minerals whereas in the Cu-rich massive sulfides the PGM formed by crystallization from late-stage fractionated sulfide liquids. We suggest that the significant amount of Sn-bearing PGM may be related to crustal contamination from granodiorite, whereas As, Bi, Te, and Sb were likely added to the magma along with S from sedimentary rocks. Large PGM that are scarce and randomly distributed may account for most of the whole-rock Pt budget. Based on our results, we propose a holistic genetic model for the formation of the magmatic sulfide ore bodies of the Noril’sk-Talnakh mining district.

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.

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.

{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.

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.

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)

Chirality-controlled spontaneous twisting of crystals due to thermal topochemical reaction.

PubMed

Rai, Rishika; Krishnan, Baiju P; Sureshan, Kana M

2018-03-20

Crystals that show mechanical response against various stimuli are of great interest. These stimuli induce polymorphic transitions, isomerizations, or chemical reactions in the crystal and the strain generated between the daughter and parent domains is transcribed into mechanical response. We observed that the crystals of modified dipeptide LL (N 3 -l-Ala-l-Val-NHCH 2 C≡CH) undergo spontaneous twisting to form right-handed twisted crystals not only at room temperature but also at 0 °C over time. Using various spectroscopic techniques, we have established that the twisting is due to the spontaneous topochemical azide-alkyne cycloaddition (TAAC) reaction at room temperature or lower temperatures. The rate of twisting can be increased by heating, exploiting the faster kinetics of the TAAC reaction at higher temperatures. To address the role of molecular chirality in the direction of twisting the enantiomer of dipeptide LL, N 3 -d-Ala-d-Val-NHCH 2 C≡CH (DD), was synthesized and topochemical reactivity and mechanoresponse of its crystals were studied. We have found that dipeptide DD not only underwent TAAC reaction, giving 1,4-triazole-linked pseudopolypeptides of d-amino acids, but also underwent twisting with opposite handedness (left-handed twisting), establishing the role of molecular chirality in controlling the direction of mechanoresponse. This paper reports ( i ) a mechanical response due to a thermal reaction and ( ii ) a spontaneous mechanical response in crystals and ( iii ) explains the role of molecular chirality in the handedness of the macroscopic mechanical response.

Hydrogen isotopic fractionation during crystallization of the terrestrial magma ocean

NASA Astrophysics Data System (ADS)

Pahlevan, K.; Karato, S. I.

2016-12-01

Models of the Moon-forming giant impact extensively melt and partially vaporize the silicate Earth and deliver a substantial mass of metal to the Earth's core. The subsequent evolution of the terrestrial magma ocean and overlying vapor atmosphere over the ensuing 105-6 years has been largely constrained by theoretical models with remnant signatures from this epoch proving somewhat elusive. We have calculated equilibrium hydrogen isotopic fractionation between the magma ocean and overlying steam atmosphere to determine the extent to which H isotopes trace the evolution during this epoch. By analogy with the modern silicate Earth, the magma ocean-steam atmosphere system is often assumed to be chemically oxidized (log fO2 QFM) with the dominant atmospheric vapor species taken to be water vapor. However, the terrestrial magma ocean - having held metallic droplets in suspension - may also exhibit a much more reducing character (log fO2 IW) such that equilibration with the overlying atmosphere renders molecular hydrogen the dominant H-bearing vapor species. This variable - the redox state of the magma ocean - has not been explicitly included in prior models of the coupled evolution of the magma ocean-steam atmosphere system. We find that the redox state of the magma ocean influences not only the vapor speciation and liquid-vapor partitioning of hydrogen but also the equilibrium isotopic fractionation during the crystallization epoch. The liquid-vapor isotopic fractionation of H is substantial under reducing conditions and can generate measurable D/H signatures in the crystallization products but is largely muted in an oxidizing magma ocean and steam atmosphere. We couple equilibrium isotopic fractionation with magma ocean crystallization calculations to forward model the behavior of hydrogen isotopes during this epoch and find that the distribution of H isotopes in the silicate Earth immediately following crystallization represents an oxybarometer for the terrestrial magma ocean. Whether such endogenous isotopic heterogeneity would survive as an observable signature in the modern silicate Earth is an open question.

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.

Ar-Ar and I-Xe Ages of Caddo County and Thermal History of IAB Iron Meteorites

NASA Technical Reports Server (NTRS)

Bogard, Donald D.; Garrison, Daniel H.; Takeda, Hiroshi

2005-01-01

Inclusions in IAB iron meteorites include non-chondritic silicate and those with more primitive chondritic silicate composition. Coarse-grained gabbroic material rich in plagioclase and diopside occurs in the Caddo County IAB iron meteorite and represents a new type of chemically differentiated, extra-terrestrial, andesitic silicate. Other parts of Caddo contain mostly andesitic material. Caddo thus exhibits petrologic characteristics of parent body metamorphism of a chondrite-like parent and inhomogeneous segregation of melts. Proposed IAB formation models include parent body partial melting and fractional crystallization or incomplete differentiation due to internal heat sources, and impact/induced melting and mixing. Benedix et al. prefer a hybrid model whereby the IAB parent body largely melted, then underwent collisional breakup, partial mixing of phases, and reassembly. Most reported 129I- Xe-129 ages of IABs are greater than 4.56 Gyr and a few are greater than or = 4.567 Gyr. These oldest ages exceed the 4.567 Gyr Pb-Pb age of Ca, Al-rich inclusions in primitive meteorites,

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.

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

Decolorization of Malachite Green and Crystal Violet by Waterborne Pathogenic Mycobacteria

PubMed Central

Jones, Jefferson J.; Falkinham III, Joseph O.

2003-01-01

Mycobacterium avium, Mycobacterium intracellulare, Mycobacterium scrofulaceum, Mycobacterium marinum, and Mycobacterium chelonae tolerate high concentrations of the dyes malachite green and crystal violet. Cells of strains of those species decolorized (reduced) both malachite green and crystal violet. Because decolorized malachite green lacked antimicrobial activity, the resistance of these mycobacteria could be due, in part, to their ability to decolorize the dyes. Small amounts of malachite green and its reduced, decolorized product were detected in the lipid fraction of M. avium strain A5 cells grown in the presence of malachite green, suggesting that a minor component of resistance could be due to sequestering the dyes in the extensive mycobacterial cell surface lipid. The membrane fraction of M. avium strain A5 had at least a fivefold-higher specific decolorization rate than did the crude extract, suggesting that the decolorization activity is membrane associated. The malachite green-decolorizing activity of the membrane fraction of M. avium strain A5 was abolished by either boiling or proteinase exposure, suggesting that the decolorizing activity was due to a protein. Decolorization activity of membrane fractions was stimulated by ferrous ion and inhibited by dinitrophenol and metyrapone. PMID:12821489

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.

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.

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.

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.

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.

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

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.

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.

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

Imaging and engineering the nanoscale-domain structure of a Sr0.61Ba0.39Nb2O6 crystal using a scanning force microscope

NASA Astrophysics Data System (ADS)

Terabe, K.; Takekawa, S.; Nakamura, M.; Kitamura, K.; Higuchi, S.; Gotoh, Y.; Gruverman, A.

2002-09-01

We have investigated the ferroelectric domain structure formed in a Sr0.61Ba0.39Nb2O6 single crystal by cooling the crystal through the Curie point. Imaging the etched surface structure using a scanning force microscope (SFM) in both the topographic mode and the piezoresponse mode revealed that a multidomain structure of nanoscale islandlike domains was formed. The islandlike domains could be inverted by applying an appropriate voltage using a conductive SFM tip. Furthermore, a nanoscale periodically inverted-domain structure was artificially fabricated using the crystal which underwent poling treatment.

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.

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.

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.

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.

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.

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.

Stoichiometric sensing to opt between gelation and crystallization.

PubMed

Vidyasagar, Adiyala; Sureshan, Kana M

2015-10-05

A new class of organogelators having a cyclohexane-1a,3a-diol motif capable of congealing non-polar liquids was developed. These gelators underwent crystallization at low concentration and gelation above the critical gelation concentration (CGC) in the same solvent. The crystals and gel fibers were analyzed by single crystal XRD and PXRD respectively, which revealed their different modes of assembly. The XRD studies and thermogravimetric analysis (TGA) confirmed that the crystals contain a water of crystallization whereas the gel fibers do not. A systematic study revealed that when the concentration of the gelator exceeds that of adventitious water in the solvent, it congeals the solvent and when the concentration of the gelator is less than water, it undergoes crystallization. This unprecedented stoichiometric sensing behavior in deciding the mode of self-assembly offers a handle to opt between mutually competing gelation and crystallization. We have confirmed that the system can be biased to congeal or crystallize by varying the amount of water. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Aqueous trifluorethanol solutions simulate the environment of DNA in the crystalline state.

PubMed

Kypr, J; Chládková, J; Zimulová, M; Vorlícková, M

1999-09-01

We took 28 fragments of DNA whose crystal structures were known and used CD spectroscopy to search for conditions stabilising the crystal structures in solution. All 28 fragments switched into their crystal structures in 60-80% aqueous trifluorethanol (TFE) to indicate that the crystals affected the conformation of DNA like the concentrated TFE. The fragments crystallising in the B-form also underwent cooperative TFE-induced changes that took place within the wide family of B-form structures, suggesting that the aqueous and crystal B-forms differed as well. Spermine and magnesium or calcium cations, which were contained in the crystallisation buffers, promoted or suppressed the TFE-induced changes of several fragments to indicate that the crystallisation agents can decide which of the possible structures is adopted by the DNA fragment in the crystal.

Intensity Modulated Radiation Therapy With Dose Painting to Treat Rhabdomyosarcoma

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

Yang, Joanna C.; Dharmarajan, Kavita V.; Wexler, Leonard H.

Purpose: To examine local control and patterns of failure in rhabdomyosarcoma patients treated with intensity modulated radiation therapy (RT) with dose painting (DP-IMRT). Patients and Methods: A total of 41 patients underwent DP-IMRT with chemotherapy for definitive treatment. Nineteen also underwent surgery with or without intraoperative RT. Fifty-six percent had alveolar histologic features. The median interval from beginning chemotherapy to RT was 17 weeks (range, 4-25). Very young children who underwent second-look procedures with or without intraoperative RT received reduced doses of 24-36 Gy in 1.4-1.8-Gy fractions. Young adults received 50.4 Gy to the primary tumor and lower doses ofmore » 36 Gy in 1.8-Gy fractions to at-risk lymph node chains. Results: With 22 months of median follow-up, the actuarial local control rate was 90%. Patients aged {<=}7 years who received reduced overall and fractional doses had 100% local control, and young adults had 79% (P=.07) local control. Three local failures were identified in young adults whose primary target volumes had received 50.4 Gy in 1.8-Gy fractions. Conclusions: DP-IMRT with lower fractional and cumulative doses is feasible for very young children after second-look procedures with or without intraoperative RT. DP-IMRT is also feasible in adolescents and young adults with aggressive disease who would benefit from prophylactic RT to high-risk lymph node chains, although dose escalation might be warranted for improved local control. With limited follow-up, it appears that DP-IMRT produces local control rates comparable to those of sequential IMRT in patients with rhabdomyosarcoma.« less

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.

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.

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.

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.

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.

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

Comparison of Causes of Death After Heart Transplantation in Patients With Left Ventricular Ejection Fractions ≤35% Versus >35.

PubMed

Birati, Edo Y; Mathelier, Hansie; Molina, Maria; Hanff, Thomas C; Mazurek, Jeremy A; Atluri, Pavan; Acker, Michael A; Rame, J Eduardo; Margulies, Kenneth B; Goldberg, Lee R; Jessup, Mariell

2016-04-15

Sudden cardiac death (SCD) is a common cause of death in the general population, occurring in 300,000 to 350,000 people in the United States alone. Currently, there are no data supporting implantable cardioverter-defibrillator therapy in patients who underwent orthotopic heart transplant (OHT) with low left ventricular ejection fraction (LVEF). In this retrospective study, we included all patients who underwent primary OHT at our institution from 2007 to 2013. We compared the cause of death in patients who underwent OHT and evaluated the correlation of the cause of death and the patients' LVEF. Our objectives were to determine whether patients who underwent OHT with LVEF <35% are at increased risk for SCD compared with those who underwent OHT with normal LVEF. To summarize our results, a total of 345 patients were included in our study (mean age 50 ± 14 years, 68% men). The mean follow-up was 1,260 ± 698 days. Forty patients (11.5%) died >6 months after OHT. Surviving patients had higher LVEF compared with deceased patients (64 ± 7% and 50 ± 24%, respectively, p ≤0.001). In all, 10 (25%) of the deceased patients died suddenly, 9 (23%) from sepsis, and 8 (20%) from malignancy. Of the 11 deceased patients with LVEF ≤35%, 2 patients (18%) died suddenly compared with 9 SCDs among the 29 deceased patients (31%) with LVEF >35% (p = 0.54). In conclusion, patients who underwent OHT who died were more likely to have LVEF <35%, and a quarter of the deceased patients who underwent OHT died suddenly. A reduced LVEF was not associated with an increased risk of SCD. Copyright © 2016 Elsevier Inc. All rights reserved.

The Kalatongke magmatic Ni-Cu deposits in the Central Asian Orogenic Belt, NW China: product of slab window magmatism?

NASA Astrophysics Data System (ADS)

Li, Chusi; Zhang, Mingjie; Fu, Piaoer; Qian, Zhuangzhi; Hu, Peiqing; Ripley, Edward M.

2012-01-01

The Permian Kalatongke Ni-Cu deposits in the Central Asian Orogenic Belt are among the most important Ni-Cu deposits in northern Xinjiang, western China. The deposits are hosted by three small mafic intrusions comprising mainly norite and diorite. Its tectonic context, petrogenesis, and ore genesis have been highly contested. In this paper, we present a new model involving slab window magmatism for the Kalatongke intrusions. The origin of the associated sulfide ores is explained in the context of this new model. Minor amounts of olivine in the intrusions have Fo contents varying between 71 and 81.5 mol%, which are similar to the predicted values for olivine crystallizing from coeval basalts in the region. Analytic modeling based on major element concentrations suggests that the parental magma of the Kalatongke intrusions and the coeval basalts represent fractionated liquids produced by ˜15% of olivine crystallization from a primary magma, itself produced by 7-8% partial melting of depleted mantle peridotite. Positive ɛ Nd values (+4 to +10) and significant negative Nb anomalies for both intrusive and extrusive rocks can be explained by the mixing of magma derived from depleted mantle with 6-18% of a partial melt derived from the lower part of a juvenile arc crust with a composition similar to coeval A-type granites in the region, plus up to 10% contamination with the upper continental crust. Our model suggests that a slab window was created due to slab break-off during a transition from oceanic subduction to arc-arc or arc-continent collision in the region in the Early Permian. Decompression melting in the upwelling oceanic asthenosphere produced the primary magma. When this magma ascended to pond in the lower parts of a juvenile arc crust, it underwent olivine crystallization and at the same time triggered partial melting of the arc crust. Mixing between these two magmas followed by contamination with the upper crust after the magma ascended to higher crustal levels formed the parental magma of the Kalatongke intrusions. The parental magma of the Kalatongke intrusions was saturated with sulfide upon arrival primarily due to olivine fractional crystallization and selective assimilation of crustal sulfur. Sulfide mineralization in the Kalatongke intrusions can be explained by accumulation of immiscible sulfide droplets by flow differentiation, gravitational settling, and downward percolation which operated in different parts of the intrusions. Platinum-group element (PGE) depletion in the bulk sulfide ores of the Kalatongke deposits was due to depletion in the parental magma which in turn was likely due to depletion in the primary magma. PGE depletion in the primary magma can be explained by a relatively low degree of partial melting of the mantle and retention of coexisting sulfide liquid in the mantle.

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.

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

In situ Raman and synchrotron X-ray diffraction study on crystallization of Choline chloride/Urea deep eutectic solvent under high pressure

NASA Astrophysics Data System (ADS)

Yuan, Chaosheng; Chu, Kunkun; Li, Haining; Su, Lei; Yang, Kun; Wang, Yongqiang; Li, Xiaodong

2016-09-01

Pressure-induced crystallization of Choline chloride/Urea (ChCl/Urea) deep eutectic solvent (DES) has been investigated by in-situ Raman spectroscopy and synchrotron X-ray diffraction. The results indicated that high pressure crystals appeared at around 2.6 GPa, and the crystalline structure was different from that formed at ambient pressure. Upon increasing the pressure, the Nsbnd H stretching modes of Urea underwent dramatic change after liquid-solid transition. It appears that high pressures may enhance the hydrogen bonds formed between ChCl and Urea. P versus T phase diagram of ChCl/Urea DES was constructed, and the crystallization mechanism of ChCl/Urea DES was discussed in view of hydrogen bonds.

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...

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.

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

Mortality following single-fraction stereotactic body radiation therapy for central pulmonary oligometastasis

PubMed Central

Ma, Sung Jun; Mix, Michael; Rivers, Charlotte; Hennon, Mark; Gomez, Jorge

2017-01-01

The case of a 56-year-old male who developed bronchopulmonary hemorrhage after a course of stereotactic body radiation therapy (SBRT) for centrally located squamous cell lung carcinoma is presented. The patient was previously treated with concurrent chemoradiation for stage IVA squamous cell carcinoma of the base of tongue. He showed no evidence of disease for 4 years until he developed a solitary metastasis of squamous cell carcinoma in the right hilum. He underwent a single fraction of 26 Gy with heterogeneity correction. He showed no evidence of disease for 13 months until he developed a sudden grade 4 bronchopulmonary hemorrhage. He underwent an urgent right pneumonectomy and later died of a post-operative complication. Pathologic analysis of the specimen revealed no evidence of tumor. Single-fraction SBRT of 26 Gy was sufficient to achieve complete response of his large central lung tumor. However, when treating patients with central lung tumors, some risk of mortality may be unavoidable with either SBRT or pneumonectomy. PMID:29296456

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

USGS Publications Warehouse

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

2008-01-01

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

Awake craniotomy in a patient with ejection fraction of 10%: considerations of cerebrovascular and cardiovascular physiology.

PubMed

Meng, Lingzhong; Weston, Stephen D; Chang, Edward F; Gelb, Adrian W

2015-05-01

A 37-year-old man with nonischemic 4-chamber dilated cardiomyopathy and low-output cardiac failure (estimated ejection fraction of 10%) underwent awake craniotomy for a low-grade oligodendroglioma resection under monitored anesthesia care. The cerebrovascular and cardiovascular physiologic challenges and our management of this patient are discussed. Published by Elsevier Inc.

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.

Visible Light Responsive Liquid Crystal Polymers Containing Reactive Moieties with Good Processability.

PubMed

Liu, Yuyun; Wu, Wei; Wei, Jia; Yu, Yanlei

2017-01-11

Two types of novel reactive linear liquid crystal polymers (LLCPs) with different azotolene concentrations have been synthesized and processed into films and fibers by solution and melting processing methods. Then, the LLCPs in the obtained monodomain fiber and polydomain film were easily cross-linked with difunctional primary amines. The resulted cross-linked liquid crystal polymers (CLCPs) underwent reversible photoinduced bending and unbending behaviors in response to 445 and 530 nm visible light at room temperature, respectively. The post-cross-linking method provides a facile way to prepare the CLCP films and fibers with different shapes from LLCPs, which can be processed by traditional melting and solution methods.

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.

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.

Short-circuiting magma differentiation from basalt straight to rhyolite?

NASA Astrophysics Data System (ADS)

Ruprecht, P.; Winslow, H.

2017-12-01

Silicic magmas are the product of varying degrees of crystal fractionation and crustal assimilation/melting. Both processes lead to differentiation that is step-wise rather than continuous for example during melt separation from a crystal mush (Dufek and Bachmann, 2010). However, differentiation is rarely efficient enough to evolve directly from a basaltic to a rhyolitic magma. At Volcán Puyehue-Cordón Caulle, Chile, the magma series is dominated by crystal fractionation where mixing trends between primitive and felsic end members in the bulk rock compositions are almost absent (e.g. P, FeO, TiO2 vs. SiO2). How effective fraction is in this magmatic system is not well-known. The 2011-12 eruption at Cordón Caulle provides new constraints that rhyolitic melts may be derived directly from a basaltic mush. Minor, but ubiquitous mafic, crystal-rich enclaves co-erupted with the predominantly rhyolitic near-aphyric magma. These enclaves are among the most primitive compositions erupted at Puyehue-Cordón Caulle and geochemically resemble closely basaltic magmas that are >10 ka old (Singer et al. 2008) and that have been identified as a parental tholeiitic mantle-derived magma (Schmidt and Jagoutz, 2017) for the Southern Andean Volcanic Zone. The vesiculated nature, the presence of a microlite-rich groundmass, and a lack of a Eu anomaly in these encalves suggest that they represent recharge magma/mush rather than sub-solidus cumulates and therefore have potentially a direct petrogenetic link to the erupted rhyolites. Our results indicate that under some conditions crystal fractionation can be very effective and the presence of rhyolitic magmas does not require an extensive polybaric plumbing system. Instead, primitive mantle-derived magmas source directly evolved magmas. In the case, of the magma system beneath Puyehue-Cordón Caulle, which had three historic rhyolitic eruptions (1921-22, 1960, 2011-12) these results raise the question whether rhyolite magma extraction has been efficient for multiple eruptions? References: Dufek & Bachmann (2010) Geology 38, 687-690; Schmidt & Jagoutz (2017) G-cubed, doi: 10.1002/2016GC006699; Singer et al. (2008) GSA Bulletin 120, 599-618.

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.

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.

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.

Magneto-optical properties of biogenic photonic crystals in algae

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

Iwasaka, M., E-mail: iwasaka-m@umin.ac.jp; Japan Science and Technology Agency, PRESTO, 4-1-8 Honcho, Kawaguchi 332-0012 Saitama; Mizukawa, Y.

In the present study, the effects of strong static magnetic fields on the structural colors of the cell covering crystals on a microalgae, coccolithophore, were investigated. The coccolithophore, Emiliania huxleyi, generates a precise assembly of calcite crystals called coccoliths by biomineralization. The coccoliths attached to the cells exhibited structural colors under side light illumination, and the colors underwent dynamic transitions when the magnetic fields were changed between 0 T and 5 T, probably due to diamagnetically induced changes of their inclination under the magnetic fields. The specific light-scattering property of individual coccoliths separated from the cells was also observed. Light scattering frommore » a condensed suspension of coccoliths drastically decreased when magnetic fields of more than 4 T were applied parallel to the direction of observation. The magnetically aligned cell-covering crystals of the coccolithophores exhibited the properties of both a photonic crystal and a minimum micromirror.« less

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.

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.

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.

Origin of the Powai ankaramite, and the composition, P-T conditions of equilibration and evolution of the primary magmas of the Deccan tholeiites

NASA Astrophysics Data System (ADS)

Chatterjee, Nilanjan; Sheth, Hetu

2015-03-01

The Powai ankaramite flow from Mumbai, western Deccan Traps, contains abundant crystals of augite (En59-47Fs10-14Wo27-42, 22-40 modal %, 3-5 mm) and olivine (Fo84-74, 11-16 modal %, 1-2 mm), and minor plagioclase (An71, ~0.5 mm) embedded in a fine-grained matrix. Minor orthopyroxene (En79-77Fs16-19Wo5-4) with irregular and embayed margins is mantled by thick augite overgrowth rims. The Fe-Mg distribution between the large crystals and bulk rock shows disequilibrium, indicating that the ankaramite is a cumulate rock. The ankaramite probably formed by the intrusion of tholeiitic melt into a cumulate pile with olivine, augite, and orthopyroxene left by the crystallization of earlier magmas, resulting in orthopyroxene dissolution and subsequent precipitation of augite. Olivine-hosted melt inclusions and melts represented by the ankaramite groundmass and some associated tholeiitic dikes are multiply saturated with olivine + plagioclase + clinopyroxene at ≤6 kb according to phase equilibrium constraints. Calculations involving incremental addition of equilibrium phases to these melts and to the common aphyric tholeiites of the voluminous Ambenali and Mahabaleshwar Formations show that their primary magmas (wt% SiO2: 48-50, MgO: 9.8-11.8, and FeO: 7.2-7.9, and Mg# 70-74) last equilibrated with spinel lherzolite at ~8-13 kb (~30-49 km depths) and ~1268-1332 °C, and trace element considerations indicate ≤15 % batch melting of mantle. These tholeiitic primary magmas then underwent olivine gabbro fractionation in upper crustal magma chambers at depths ≤23 km. The minimum depth of equilibration of the primary magmas is shallower than the present-day Moho in the Mumbai area based on seismological data, indicating localized mantle upwelling and lower crustal interactions previously inferred from the Nd-Sr isotopic ratios and other geochemical characteristics of the ankaramite and associated tholeiites.

(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.

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.

Damage, Self-Healing, and Hysteresis in Spider Silks

PubMed Central

De Tommasi, D.; Puglisi, G.; Saccomandi, G.

2010-01-01

Abstract In this article, we propose a microstructure-based continuum model to describe the material behavior of spider silks. We suppose that the material is composed of a soft fraction with entropic elasticity and a hard, damageable fraction. The hard fraction models the presence of stiffer, crystal-rich, oriented regions and accounts for the effect of softening induced by the breaking of hydrogen bonds. To describe the observed presence of crystals with different size, composition, and orientation, this hard fraction is modeled as a distribution of materials with variable properties. The soft fraction describes the remaining regions of amorphous material and is here modeled as a wormlike chain. During stretching, we consider the effect of bond-breaking as a transition from the hard- to the soft-material phase. As we demonstrate, a crucial effect of bond-breaking that accompanies the softening of the material is an increase in contour length associated with chains unraveling. The model describes also the self-healing properties of the material by assuming partial bond reconnection upon unloading. Despite its simplicity, the proposed mechanical system reproduces the main experimental effects observed in cyclic loading of spider silks. Moreover, our approach is amenable to two- or three-dimensional extensions and may prove to be a useful tool in the field of microstructure optimization for bioinspired materials. PMID:20441758

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.

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.

The application of crystal soaking technique to study the effect of zinc and cresol on insulinotropin crystals grown from a saline solution.

PubMed

Kim, Y; Haren, A M

1995-11-01

The purpose of this study is to investigate the effect of zinc and cresol on the structure of insulinotropin crystals. Insulinotropin crystals grown from a saline solution were treated with zinc and/or m-cresol using a crystal soaking technique. The effects of these additives on the crystal structure were investigated with powder X-ray diffraction, photomicrography, and differential scanning calorimetry. The molecular interaction between insulinotropin and m-trifluorocresol in solution was also studied by 19F NMR: The data suggest that the original crystals grown from a saline solution have relatively weak lattice forces. After the addition of m-cresol to the suspension of the insulinotropin crystals, the crystals were immediately rendered amorphous. The m-cresol molecules which diffused into the crystals through solvent channels may have disturbed the lattice interactions that maintain the integrity of the crystal. In contrast, the zinc added to the suspension stabilized the crystal lattice so that the subsequent addition of m-cresol did not alter the integrity of the crystals. A marked increase in melting point (206 degrees versus 184 degrees) and heat of fusion (24.6 J/g versus 1.4 J/g) of the crystals was observed after the treatment with zinc. The solubility of the zinc treated crystals in a pH 7.1 phosphate buffered saline was 1/20 of that of the original crystals. When the insulinotropin crystals were treated with the additives using a crystal soaking method, the crystals underwent structural changes. Zinc stabilized the crystal lattice, and reduced the solubility of the peptide.

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

Exercise testing in asymptomatic or minimally symptomatic aortic regurgitation: relationship of left ventricular ejection fraction to left ventricular filling pressure during exercise

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

Boucher, C.A.; Wilson, R.A.; Kanarek, D.J.

Exercise radionuclide angiography is being used to evaluate left ventricular function in patients with aortic regurgitation. Ejection fraction is the most common variable analyzed. To better understand the rest and exercise ejection fraction in this setting, 20 patients with asymptomatic or minimally symptomatic severe aortic regurgitation were studied. All underwent simultaneous supine exercise radionuclide angiography and pulmonary gas exchange measurement and underwent rest and exercise measurement of pulmonary artery wedge pressure (PAWP) during cardiac catheterization. Eight patients had a peak exercise PAWP less than 15 mm Hg (group 1) and 12 had a peak exercise PAWP greater than or equalmore » to 15 mm Hg (group 2). Group 1 patients were younger and more were in New York Heart Association class I. The two groups had similar cardiothoracic ratios, changes in ejection fractions with exercise, and rest and exercise regurgitant indexes. Using multiple regression analysis, the best correlate of the exercise PAWP was peak oxygen uptake (r . -0.78, p less than 0.01). No other measurement added significantly to the regression. When peak oxygen uptake was excluded, rest and exercise ejection fraction also correlated significantly (r . -0.62 and r . -0.60, respectively, p less than 0.01). Patients with asymptomatic or minimally symptomatic severe aortic regurgitation have a wide spectrum of cardiac performance in terms of the PAWP during exercise. The absolute rest and exercise ejection fraction and the level of exercise achieved are noninvasive variables that correlate with exercise PAWP in aortic regurgitation, but the change in ejection fraction with exercise by itself is not.« less

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

Anisotropically Swelling Gels Attained through Axis-Dependent Crosslinking of MOF Crystals.

PubMed

Ishiwata, Takumi; Kokado, Kenta; Sada, Kazuki

2017-03-01

Anisotropically deforming objects have attracted considerable interest for use in molecular machines and artificial muscles. Herein, we focus on a new approach based on the crystal crosslinking of organic ligands in a pillared-layer metal-organic framework (PLMOF). The approach involves the transformation from crosslinked PLMOF to polymer gels through hydrolysis of the coordination bonds between the organic ligands and metal ions, giving a network polymer that exhibits anisotropic swelling. The anisotropic monomer arrangement in the PLMOF underwent axis-dependent crosslinking to yield anisotropically swelling gels. Therefore, the crystal crosslinking of MOFs should be a useful method for creating actuators with designable deformation properties. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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

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.

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.

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.

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.

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

Anisotropy of nickel-base superalloy single crystals

NASA Technical Reports Server (NTRS)

Mackay, R. A.; Dreshfield, R. L.; Maier, R. D.

1980-01-01

The influence of orientation on the tensile and stress rupture behavior of 52 Mar-M247 single crystals was studied. Tensile tests were performed at temperatures between 23 and 1093 C; stress rupture behavior was examined between 760 and 1038 C. The mechanical behavior of the single crystals was rationalized on the basis of the Schmid factor contours for the operative slip systems and the lattice rotations which the crystals underwent during deformation. The tensile properties correlated well with the appropriate Schmid factor contours. The stress rupture lives at lower testing temperatures were greatly influenced by the lattice rotations required to produce cross slip. A unified analysis was attained for the stress rupture life data generated for the Mar-M247 single crystals at 760 and 774 C under a stress of 724 MPa and the data reported for Mar-M200 single crystals tested at 760 C under a stress of 689 MPa. Based on this analysis, the stereographic triangle was divided into several regions which were rank ordered according to stress rupture life for this temperature regime.

Scanning electron microscopic study of a Ciloxan bottle blocked by ciprofloxacin crystals.

PubMed

John, T

2001-12-01

To report blockage of a commercially available ciprofloxacin bottle by white crystalline deposits. This study evaluated the ultrastructural features of the ciprofloxacin crystals. A patient underwent intensive topical treatment of an infectious corneal ulcer with commercially available ciprofloxacin 0.3% ophthalmic solution. During treatment, the patient was unable to obtain medication from the ciprofloxacin bottle and required a new prescription. Examination of the bottle revealed that about 50% of the medication remained, but compression of the bottle with any amount of force failed to deliver any medication. On closer examination, a white material partially filled the nozzle track of the bottle and was on the outer bottle near the nozzle and the inner surface of the bottle cap. These white crystalline deposits were evaluated by scanning electron microscopy. Plate-like, needle, cable and spaghetti-like crystals were found. The needle crystals formed multiple petaloid patterns. This is the first report of blockage of a commercially available ciprofloxacin 0.3% bottle by ciprofloxacin crystals and the inability to deliver medication from the bottle. Ultrastructural study of the white crystalline deposits revealed four types of ciprofloxacin crystals.

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.

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.

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 Jurassic peraluminous biotite granites and muscovite-bearing granites in SE China: geochronological, elemental and Sr-Nd-O-Hf isotopic constraints

NASA Astrophysics Data System (ADS)

Jiang, Yao-Hui; Zhu, Shu-Qi

2017-12-01

Biotite granites and muscovite-bearing granites are dominant rock types of the widespread granites in SE China. However, their petrogenesis has been enigmatic. A combined study of zircon U-Pb dating and Lu-Hf isotopes, whole-rock element geochemistry and Sr-Nd-O isotopes was performed for three late Mesozoic granitic plutons (Xinfengjie, Jiangbei and Dabu) in central Jiangxi province, SE China. All the plutons are composed of biotite granites and muscovite-bearing granites that have been poorly investigated previously. The new data not only allow us to assess their sources and magma evolution processes, but also helps us to better understand the genetic link to the large-scale polymetallic mineralization in SE China. LA-ICP-MS zircon U-Pb dating shows that three plutons were emplaced in the Late Jurassic (159-148 Ma) and that the muscovite-bearing granites are almost contemporaneous with the biotite granites. The biotite granites have SiO2 contents of 70.3-74.4 wt% and are weakly to strongly peraluminous with ASI from 1.00 to 1.26, and show a general decrease in ASI with increasing SiO2. They have relatively high zircon saturation temperatures ( T Zr = 707-817 °C, most > 745 °C) and show a general decrease in T Zr with increasing SiO2. They have high initial 87Sr/86Sr ratios (0.7136 to 0.7166) and high δ18O values (9.1-12.8‰, most > 9.5‰) and clearly negative ɛ Nd (T) (- 9.5 to - 11.8) and ɛ Hf (T) (in situ zircon) (- 13.1 to - 13.5). The muscovite-bearing granites have high SiO2 contents (74.7-78.2 wt%). They are also weakly to strongly peraluminous with ASI of 1.04-1.18 but show a general increase in ASI with increasing SiO2. They have relatively low T Zr (671-764 °C, most < 745 °C) and also show a general decrease in T Zr with increasing SiO2. The muscovite-bearing granites have high Rb (up to 810 ppm) and high (K2O + Na2O)/CaO (up to 270), Rb/Sr (up to 42) and Rb/Ba (up to 30) as well as low K/Rb (< 150, down to 50), Zr/Hf (< 24, down to 11) and Nb/Ta (< 6, down to 2). They show similar Nd-O-Hf isotopic compositions to the biotite granites with ɛ Nd (T) of - 8.7 to - 12.0, δ18O of 8.7-13.0‰ (most > 9.5‰) and ɛ Hf (T) (in situ zircon) of - 11.3 to - 13.1. Geochemical data suggest the origin of the biotite granites and muscovite-bearing granites as follows: Partial melting of Precambrian metasedimentary rocks (mainly two-mica schist) in the lower crust at temperatures of ca. 820 °C generated the melts of the less felsic biotite granites. Such primary crustal melts underwent biotite-dominant fractionation crystallization, forming the felsic biotite granites. Progressive plagioclase-dominant fractionation crystallization from the evolved biotite granites produced the more felsic muscovite-bearing granites. Thus, the biotite granites belong to the S-type whereas the muscovite-bearing granites are highly fractionated S-type granites. We further suggest that during the formation of the muscovite-bearing granites the fractional crystallization was accompanied by fluid fractionation and most likely the addition of internally derived mineralizing fluids. That is why the large-scale polymetallic mineralization is closely related to the muscovite-bearing granites rather than biotite granites in SE China. This is important to further understand the source and origin of biotite granites and muscovite-bearing granites in SE China even worldwide.

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.

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.

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.

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.

Geochemical and Nd-Sr-Pb isotope characteristics of synorogenic lower crust-derived granodiorites (Central Damara orogen, Namibia)

NASA Astrophysics Data System (ADS)

Simon, I.; Jung, S.; Romer, R. L.; Garbe-Schönberg, D.; Berndt, J.

2017-03-01

The 547 ± 7 Ma old Achas intrusion (Damara orogen, Namibia) includes magnesian, metaluminous to slightly peraluminous, calcic to calc-alkalic granodiorites and ferroan, metaluminous to slightly peraluminous, calc-alkalic to alkali-calcic leucogranites. For the granodiorites, major and trace element variations show weak if any evidence for fractional crystallization whereas some leucogranites are highly fractionated. Both, granodiorites and leucogranites are isotopically evolved (granodiorites: εNdinit: - 12.4 to - 20.5; TDM: 2.4-1.9; leucogranites: εNdinit: - 12.1 to - 20.6, TDM: 2.5-2.0), show similar Pb isotopic compositions, and may be derived from late Archean to Paleoproterozoic crustal source rocks. Comparison with melting experiments and simple partial melting modeling indicate that the granodiorites may be derived by extensive melting (> 40%) at 900-950 °C under water-undersaturated conditions (< 5 wt.% H2O) of felsic gneisses. Al-Ti and zircon saturation thermometry of the most primitive granodiorite sample yielded temperatures of ca. 930 °C and ca. 800 °C. In contrast to other lower crust-derived granodiorites and granites of the Central Damara orogen, the composition of the magma source is considered the first-order cause of the compositional diversity of the Achas granite. Second-order processes such as fractional crystallization at least for the granodiorites were minor and evidence for coupled assimilation-fractional crystallization processes is lacking. The most likely petrogenetic model involves high temperature partial melting of a Paleoproterozoic felsic source in the lower crust ca. 10-20 Ma before the first peak of regional high-temperature metamorphism. Underplating of the lower crust by magmas derived from the lithospheric mantle may have provided the heat for melting of the basement to produce anhydrous granodioritic melts.

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.

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

The Impact of Deep Versus Moderate Hypothermia on Postoperative Kidney Function After Elective Aortic Hemiarch Repair.

PubMed

Arnaoutakis, George J; Vallabhajosyula, Prashanth; Bavaria, Joseph E; Sultan, Ibrahim; Siki, Mary; Naidu, Suveeksha; Milewski, Rita K; Williams, Matthew L; Hargrove, W Clark; Desai, Nimesh D; Szeto, Wilson Y

2016-10-01

There remains concern that moderate hypothermic circulatory arrest (MHCA) with antegrade cerebral perfusion (ACP) may provide suboptimal distal organ protection compared with deep hypothermic circulatory arrest (DHCA) with retrograde cerebral perfusion (RCP). We compared postoperative acute kidney injury (AKI) in in patients who underwent elective hemiarch repair with either DHCA/RCP or MHCA/ACP. This was a retrospective review of all patients undergoing elective aortic hemiarch reconstruction for aneurysmal disease between 2009 and 2014. Patients were stratified according to the use of DHCA/RCP versus MHCA/ACP. The primary outcome was the occurrence of AKI at 48 hours, as defined by the Risk, Injury, Failure, Loss, End-Stage (RIFLE ) criteria. A multivariable logistic regression identified risk factors for AKI. One hundred eighteen patients who underwent ACP and 471 patients who underwent RCP were included. The mean lowest temperature was 26.4°C in patients who underwent MHCA/ACP and 17.5°C in patients who underwent DHCA/RCP. Baseline demographics were similar except that patients who underwent DHCA/RCP were more likely to have peripheral arterial disease or bicuspid aortic valves. Cardiopulmonary bypass and aortic cross-clamp times were shorter in the MHCA/ACP group. AKI occurred in 19 (16.2%) patients who underwent MHCA/ACP and 67 (14.3%) patients who underwent DHCA/RCP. Four (0.8%) patients who underwent DHCA/RCP required postoperative dialysis. In-hospital mortality tended to increase with increasing RIFLE classification (RIFLE class-0 (No AKI) = 0.41%; Risk = 1.35%, and Injury = 10.0%; p = 0.09). On multivariable analysis, the lowest temperature and cerebral perfusion strategy were not significant predictors of AKI. Lower baseline glomerular filtration rate (GFR), lower preoperative ejection fraction, and longer cardiopulmonary bypass (CPB) time were independently associated with higher AKI. We applied the sensitive RIFLE criteria to examine AKI in patients undergoing elective aortic hemiarch replacement for aneurysmal disease. Baseline renal dysfunction, lower ejection fraction, and longer CPB time are independent predictors of AKI. Compared with DHCA/RCP, our data suggest that an MHCA/ACP cerebral protection strategy does not appear to be associated with worse postoperative renal outcomes. Copyright © 2016 The Society of Thoracic Surgeons. Published by Elsevier Inc. All rights reserved.

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.

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

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

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.

Multiple brain metastases irradiation with Eleka Axesse stereotactic system

NASA Astrophysics Data System (ADS)

Filatov, P. V.; Polovnikov, E. S.; Orlov, K. Yu.; Krutko, A. V.; Kirilova, I. A.; Moskalev, A. V.; Filatova, E. V.; Zheravin, A. A.

2017-09-01

Brain metastases are one of the factors complicating the treatment of a malignant tumor. Radiation therapy, especially radiosurgery, plays an important role in the modern treatment practice. During 2011-2016, 32 patients (from 29 to 67 years old) with multiple brain metastases underwent the treatment with SRS or SRT in our center. The number of secondary lesions varied from 2 to 11. Eight patients underwent microsurgery resection. Seven patients had recurrence after whole brain radiotherapy. Thirty patient underwent single fraction SRS and two patients with large metastases (bigger than 3 cm) underwent fractionated SRT. The treatment was done with dedicated linear accelerator stereotactic system Elekta Axesse (Elekta AB, Stockholm, Sweden). Different stereotactic fixation devices were used, namely, Leksell G frame, non-invasive HeadFIX frame, and reinforced thermoplastic mask (IMRT perforation). All treatments included a volumetric modulated arc therapy (VMAT) technique and of Inage Guided Radiation Therapy (IGRT) technique. All lesions were treated from a single isocenter, which allowed reducing the treatment time and overall dose to the patient's body. All patients suffered the treatment satisfactorily. No adverse reactions or complications were met in any case during or right after the treatment. Different stereotactic fixation devices and modern treatment techniques allowed creating an optimal, safe and comfortable way for patient treatment. The treatment time was from 15 to 50 minutes. Patient position verification after or during the treatment demonstrated good accuracy for all fixation types and low level of intrafraction motion.

Benefits of Permanent His Bundle Pacing Combined With Atrioventricular Node Ablation in Atrial Fibrillation Patients With Heart Failure With Both Preserved and Reduced Left Ventricular Ejection Fraction.

PubMed

Huang, Weijian; Su, Lan; Wu, Shengjie; Xu, Lei; Xiao, Fangyi; Zhou, Xiaohong; Ellenbogen, Kenneth A

2017-04-01

Clinical benefits from His bundle pacing (HBP) in heart failure patients with preserved and reduced left ventricular ejection fraction are still inconclusive. This study evaluated clinical outcomes of permanent HBP in atrial fibrillation patients with narrow QRS who underwent atrioventricular node ablation for heart failure symptoms despite rate control by medication. The study enrolled 52 consecutive heart failure patients who underwent attempted atrioventricular node ablation and HBP for symptomatic atrial fibrillation. Echocardiographic left ventricular ejection fraction and left ventricular end-diastolic dimension, New York Heart Association classification and use of diuretics for heart failure were assessed during follow-up visits after permanent HBP. Of 52 patients, 42 patients (80.8%) received permanent HBP and atrioventricular node ablation with a median 20-month follow-up. There was no significant change between native and paced QRS duration (107.1±25.8 versus 105.3±23.9 milliseconds, P =0.07). Left ventricular end-diastolic dimension decreased from the baseline ( P <0.001), and left ventricular ejection fraction increased from baseline ( P <0.001) in patients with a greater improvement in heart failure with reduced ejection fraction patients (N=20) than in heart failure with preserved ejection fraction patients (N=22). New York Heart Association classification improved from a baseline 2.9±0.6 to 1.4±0.4 after HBP in heart failure with reduced ejection fraction patients and from a baseline 2.7±0.6 to 1.4±0.5 after HBP in heart failure with preserved ejection fraction patients. After 1 year of HBP, the numbers of patients who used diuretics for heart failure decreased significantly ( P <0.001) when compared to the baseline diuretics use. Permanent HBP post-atrioventricular node ablation significantly improved echocardiographic measurements and New York Heart Association classification and reduced diuretics use for heart failure management in atrial fibrillation patients with narrow QRS who suffered from heart failure with preserved or reduced ejection fraction. © 2017 The Authors. Published on behalf of the American Heart Association, Inc., by Wiley Blackwell.

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.

Experimental study on the Neapolitan Yellow Tuff: Salt weathering and consolidation

NASA Astrophysics Data System (ADS)

La Russa, Mauro Francesco; Ruffolo, Silvestro Antonio; Alvarez de Buergo, Monica; Ricca, Michela; Belfiore, Cristina Maria; Pezzino, Antonino; Mirocle Crisci, Gino

2016-04-01

Salt crystallization is one of the major weathering agents in porous building materials due to the crystallization pressure exerted by salt crystals growing in confined pores. The consolidation of such degraded stone materials is a crucial issue in the field of Cultural Heritage restoration. This contribution deals with laboratory experimentation carried out on the Neapolitan Tuff, a pyroclastic rock largely used in the Campanian architecture. Several specimens, collected from a historical quarry nearby the city of Naples, were treated with two different consolidating products: a suspension of nanosilica in water (Syton X30®) and ethyl silicate (Estel 1000®) dispersed in organic solvent (TEOS). Then, in order to assess the effectiveness of consolidation treatments, both treated and untreated samples underwent accelerated degradation through salt crystallization tests. A multi-analytical approach, including mercury intrusion porosimetry, peeling tests and point load test, was employed to evaluate the correlation between the salt crystallization and the micro-structural features of the examined tuff specimens. In addition, the calculation of the crystallization pressures was also performed in order to make a correlation between the porous structure of the tuff and its susceptivity to salt crystallization. Obtained results show that both the tested products increase the resistance of tuff to salt crystallization, although inducing an increase of crystallization pressure. Ethyl silicate, however, shows a better behaviour in terms of superficial cohesion, even after several degradation cycles.

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.

SU-C-202-02: A Comprehensive Evaluation of Adaptive Daily Planning for Cervical Cancer HDR Brachytherapy

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

Meerschaert, R; Paul, A; Zhuang, L

Purpose: To evaluate adaptive daily planning for cervical cancer patients who underwent high-dose-rate intra-cavitary brachytherapy (HDR-ICBT). Methods: This study included 22 cervical cancer patients who underwent 5 fractions of HDR ICBT. Regions of interest (ROIs) including high-risk clinical tumor volume (HR-CTV) and organs-at-risk (OARs) were manually contoured on daily CT images. All patients were treated with adaptive daily plans, which involved ROI delineation and dose optimization at each treatment fraction. Single treatment plans were retrospectively generated by applying the first treatment fraction’s dwell times adjusted for decay and dwell positions of the applicator to subsequent treatment fractions. Various existing similaritymore » metrics were calculated for the ROIs to quantify interfractional organ variations. A novel similarity score (JRARM) was established, which combined both volumetric overlap metrics (DSC, JSC, and RVD) and distance metrics (ASD, MSD, and RMSD). Linear regression was performed to determine a relationship between inter-fractional organ variations of various similarity metrics and D2cc variations from both plans. Wilcoxon Signed Rank Tests were used to assess adaptive daily plans and single plans by comparing EQD2 D2cc (α/β=3) for OARs. Results: For inter-fractional organ variations, the sigmoid demonstrated the greatest variations based on the JRARM and DSC similarity metrics. Comparisons between paired ROIs showed differences in JRARM scores and DSCs at each treatment fraction. RVD, MSD, and RMSD were found to be significantly correlated to D2cc variations for bladder and sigmoid. The comparison between plans found that adaptive daily planning provided lower EQD2 D2cc of OARs than single planning, specifically for the sigmoid (p=0.015). Conclusion: Substantial inter-fractional organ motion can occur during HDR-BT, which may significantly affect D2cc of OARs. Adaptive daily planning provides improved dose sparing for OARs compared to single planning.« less

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.

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.

Structure and phase formation behavior and dielectric and magnetic properties of lead iron tantalate-lead zirconate titanate multiferroic ceramics

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

Wongmaneerung, R., E-mail: re_nok@yahoo.com; Tipakontitikul, R.; Jantaratana, P.

2016-03-15

Highlights: • The multiferroic ceramics consisted of PFT and PZT. • Crystal structure changed from cubic to mixedcubic and tetragonal with increasing PZT content. • Dielectric showed the samples underwent a typical relaxor ferroelectric behavior. • Magnetic properties showed very interesting behavior with square saturated magnetic hysteresis loops. - Abstract: Multiferroic (1 − x)Pb(Fe{sub 0.5}Ta{sub 0.5})O{sub 3}–xPb(Zr{sub 0.53}Ti{sub 0.47})O{sub 3} (or PFT–PZT) ceramics were synthesized by solid-state reaction method. The crystal structure and phase formation of the ceramics were examined by X-ray diffraction (XRD). The local structure surrounding Fe and Ti absorbing atoms was investigated by synchrotron X-ray Absorption Near-Edgemore » Structure (XANES) measurement. Dielectric properties were studied as a function of frequency and temperature using a LCR meter. A vibrating sample magnetometer (VSM) was used to determine the magnetic hysteresis loops. XRD study indicated that the crystal structure of the sample changed from pure cubic to mixed cubic and tetragonal with increasing PZT content. XANES measurements showed that the local structure surrounding Fe and Ti ions was similar. Dielectric study showed that the samples underwent a typical relaxor ferroelectric behavior while the magnetic properties showed very interesting behavior with square saturated magnetic hysteresis loops.« less

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.

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.

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.

The magma plumbing system in the Mariana Trough back-arc basin at 18° N

NASA Astrophysics Data System (ADS)

Lai, Zhiqing; Zhao, Guangtao; Han, Zongzhu; Huang, Bo; Li, Min; Tian, Liyan; Liu, Bo; Bu, Xuejiao

2018-04-01

Mafic magmas are common in back-arc basin, once stalled in the crust, these magmas may undergo different evolution. In this paper, compositional and textural variations of plagioclase as well as mineral-melt geothermobarometry are presented for basalts erupted from the central Mariana Trough (CMT). These data reveal crystallization conditions and we attempt a reconstruction of the magma plumbing system of the CMT. Plagioclase megacrysts, phenocrysts, microphenocrysts, microlites, olivine, spinel, and clinopyroxene have been recognized in basalt samples, using BSE images and compositional features. The last three minerals are homogeneous as microphenocrysts. Mineral-melt barometry indicates that plagioclase crystals crystallized and eventually grew into phenocrysts and megacrysts in mush zone with depth of 5-9 km, in which the normal zoning plagioclases crystallized in the interval of various batches of basic magma recharging. Plagioclase megacrysts and phenocrysts were dissolved and/or resorbed, when new basic magmas injected into the mush zone near Moho depth. It is inferred that magma extracted from the mush zone, and adiabatically ascended via different pathways. Some basaltic magmas underwent plagioclase and clinopyroxene microphenocrysts crystallization in low-pressure before eruption. Plagioclase microlites and outermost rims probably crystallized after eruption.

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.

Crystallization processes in Ge{sub 2}Sb{sub 2}Se{sub 4}Te glass

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

Svoboda, Roman, E-mail: roman.svoboda@upce.cz; Bezdička, Petr; Gutwirth, Jan

2015-01-15

Highlights: • Crystallization kinetics of Ge{sub 2}Sb{sub 2}Se{sub 4}Te glass was studied in dependence on particle size by DSC. • All studied fractions were described in terms of the SB autocatalytic model. • Relatively high amount of Te enhances manifestation of bulk crystallization mechanisms. • XRD analysis of samples crystallized under different conditions showed correlation with DSC data. • XRD analysis revealed a new crystallization mechanism indistinguishable by DSC. - Abstract: Differential scanning calorimetry (DSC) and X-ray diffraction (XRD) analysis were used to study crystallization in Ge{sub 2}Sb{sub 2}Se{sub 4}Te glass under non-isothermal conditions as a function of the particlemore » size. The crystallization kinetics was described in terms of the autocatalytic Šesták–Berggren model. An extensive discussion of all aspects of a full-scale kinetic study of a crystallization process was undertaken. Dominance of the crystallization process originating from mechanically induced strains and heterogeneities was confirmed. Substitution of Se by Te was found to enhance the manifestation of the bulk crystallization mechanisms (at the expense of surface crystallization). The XRD analysis showed significant dependence of the crystalline structural parameters on the crystallization conditions (initial particle size of the glassy grains and applied heating rate). Based on this information, a new microstructural crystallization mechanism, indistinguishable by DSC, was proposed.« less

Endoscopic Pilonidal Sinus Treatment Combined With Crystalized Phenol Application May Prevent Recurrence.

PubMed

Gecim, Ibrahim Ethem; Goktug, Utku Ufuk; Celasin, Haydar

2017-04-01

No single treatment yet exists for pilonidal disease that has a short healing time, good cosmetic results, and a low rate of recurrence. Phenol crystal application and diathermy ablation through an endoscope have been used for the treatment of pilonidal disease, but this cohort is the first one to combine them. The purpose of this study was to examine the safety, effectiveness, and short- and long-term outcomes of crystalized phenol treatment combined with endoscopic pilonidal sinus treatment for pilonidal disease. This was a prospective cohort study. Procedures were performed in 2 hospitals by the same surgeon between February and July 2014. Twenty-three patients underwent surgical treatment for pilonidal disease. Under local anesthesia and sedation, all of the patients underwent a video-assisted diathermy ablation of the sinus cavity and the application of phenol crystals. Adverse events were recorded as a measure of safety and tolerability. Failure to heal and recurrence rate were documented and evaluated. Patients were discharged on the same day as surgery. There was no or minimal postoperative pain (mean visual analog scale score, 1.40 ± 0.95). Mean operation time was 20.43 ± 6.19 minutes, and the median return-to-work duration was 2.00 days (mean, 3.03 ± 2.95 d). Patients were followed-up for 18 to 24 months (mean, 22.00 ± 1.88 mo). No serious complications or rehospitalization were observed. No primary failure to heal or recurrence was observed. This study did not include a control group with which to compare and consisted of a relatively small number of patients. Crystalized phenol treatment combined with endoscopic pilonidal sinus treatment was safe, tolerable, and achieved fast and durable healing with no recurrence over an average of 22 months of follow-up.

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.

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

Petrogenesis of a Mesoproterozoic shoshonitic lamprophyre dyke from the Wajrakarur kimberlite field, eastern Dharwar craton, southern India: Geochemical and Sr-Nd isotopic evidence for a modified sub-continental lithospheric mantle source

NASA Astrophysics Data System (ADS)

Pandey, Ashutosh; Chalapathi Rao, N. V.; Chakrabarti, Ramananda; Pandit, Dinesh; Pankaj, Praveer; Kumar, Alok; Sahoo, Samarendra

2017-11-01

Mineralogy and geochemistry of the Udirpikonda lamprophyre, located within the Mesoproterozoic diamondiferous Wajrakarur kimberlite field (WKF), towards the western margin of the Paleo-Mesoproterozoic Cuddapah basin are presented. The lamprophyre is characterised by a panidiomorphic-porphyritic texture imparted by clinopyroxene, olivine and biotite set in a groundmass of feldspar and spinel. Olivine occurs as the microphenocrysts with a composition range of Fo87-78. Clinopyroxenes display reverse as well as oscillatory optical zoning and are diopsidic in nature with a variation in the composition from core (Wo47 En28 Fs20Ac5) to rim (Wo46En41Fs11Ac3). Biotite (Mg# < 0.6) is the only mica present and spinels are titano-magnetites showing ulvospinel- magnetite solid solution. Plagioclase is the dominant feldspar with a variable compositional range of An41-8Ab82-56Or33-3. Based on the mineralogy, the lamprophyre can be classified to be of calc-alkaline variety but its geochemistry display mixed signals of both alkaline and calc-alkaline lamprophyres. K2O/Na2O ranges from 1.49 to 2.79, making it distinctly potassic and highlights its shoshonitic character. Moderate Mg# (60-65), Ni (110-200 ppm) and Cr (110-260 ppm) contents in the bulk-rock indicate substantial fractional crystallization of olivine and clinopyroxene. Fractionated chondrite normalized REE patterns (average (La/Yb)N = 37.56) indicates involvement of an enriched mantle source from within the garnet stability field whereas slightly negative Ta-Nb-Ti and Hf anomalies displayed on the primitive mantle normalized multi-element spider gram highlight involvement of a subducted component in the mantle source. Given the spatial disposition of the studied lamprophyre, the age of the emplacement is considered to be coeval with WKF kimberlites ( 1.1 Ga) and the initial 143Nd/144Nd (0.510065-0.510192) and 87Sr/86Sr (0.705333-0.706223) are strikingly similar to those observed for the Smoky Butte lamproites, Montana, USA. Fluid-related subduction enrichment of the mantle source is apparent from the enriched ratios of La/Nb, Ba/Nb and (Hf/Sm)N, (Ta/La)N < 1. Petrogenetic modelling reveals melt generation from 1 to 2% partial melting of an enriched mantle source that subsequently underwent fractional crystallization. Our study provides geochemical and isotopic evidence for a sub-continental lithospheric mantle (SCLM) modified by subduction and asthenospheric upwelling in the Eastern Dharwar Craton. The partial melting of a resulting heterogeneous Eastern Dharwar Craton SCLM to generate Udiripikonda lamprophyre and Wajrakarur kimberlites has been attributed to the Mesoproterozoic regional lithospheric extension event.

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.

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.

High-dose-rate brachytherapy – a novel treatment approach for primary clear cell adenocarcinoma of male urethra

PubMed Central

Lewis, Shirley; Pal, Mahendra; Bakshi, Ganesh; Ghadi, Yogesh G.; Menon, Santosh; Murthy, Vedang

2015-01-01

The incidence of male urethral cancer is rare with age preponderance of 50 to 60 years. The standard management approach is surgery. Here, we present a novel treatment approach for male urethral cancer. Thirty-six year old male, case of primary clear cell adenocarcinoma of urethra who refused surgery, underwent cystoscopic assisted intraluminal HDR brachytherapy. Patient received a dose of 36 Gy in 9 fractions (4 Gy per fraction) followed by a boost of 24 Gy in 6 fractions. At 11 months post treatment, disease is well controlled with no post treatment toxicity so far. Intraluminal brachytherapy seems to be an effective novel treatment for male urethral cancer. PMID:26207115

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.

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.

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.

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.

Reduced ventral cingulum integrity and increased behavioral problems in children with isolated optic nerve hypoplasia and mild to moderate or no visual impairment.

PubMed

Webb, Emma A; O'Reilly, Michelle A; Clayden, Jonathan D; Seunarine, Kiran K; Dale, Naomi; Salt, Alison; Clark, Chris A; Dattani, Mehul T

2013-01-01

To assess the prevalence of behavioral problems in children with isolated optic nerve hypoplasia, mild to moderate or no visual impairment, and no developmental delay. To identify white matter abnormalities that may provide neural correlates for any behavioral abnormalities identified. Eleven children with isolated optic nerve hypoplasia (mean age 5.9 years) underwent behavioral assessment and brain diffusion tensor imaging, Twenty four controls with isolated short stature (mean age 6.4 years) underwent MRI, 11 of whom also completed behavioral assessments. Fractional anisotropy images were processed using tract-based spatial statistics. Partial correlation between ventral cingulum, corpus callosum and optic radiation fractional anisotropy, and child behavioral checklist scores (controlled for age at scan and sex) was performed. Children with optic nerve hypoplasia had significantly higher scores on the child behavioral checklist (p<0.05) than controls (4 had scores in the clinically significant range). Ventral cingulum, corpus callosum and optic radiation fractional anisotropy were significantly reduced in children with optic nerve hypoplasia. Right ventral cingulum fractional anisotropy correlated with total and externalising child behavioral checklist scores (r = -0.52, p<0.02, r = -0.46, p<0.049 respectively). There were no significant correlations between left ventral cingulum, corpus callosum or optic radiation fractional anisotropy and behavioral scores. Our findings suggest that children with optic nerve hypoplasia and mild to moderate or no visual impairment require behavioral assessment to determine the presence of clinically significant behavioral problems. Reduced structural integrity of the ventral cingulum correlated with behavioral scores, suggesting that these white matter abnormalities may be clinically significant. The presence of reduced fractional anisotropy in the optic radiations of children with mild to moderate or no visual impairment raises questions as to the pathogenesis of these changes which will need to be addressed by future studies.

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

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.

Origin of metaluminous and alkaline volcanic rocks of the Latir volcanic field, northern Rio Grande rift, New Mexico

USGS Publications Warehouse

Johnson, C.M.; Lipman, P.W.

1988-01-01

Volcanic rocks of the Latir volcanic field evolved in an open system by crystal fractionation, magma mixing, and crustal assimilation. Early high-SiO2 rhyolites (28.5 Ma) fractionated from intermediate compositionmagmas that did not reach the surface. Most precaldera lavas have intermediate-compositions, from olivine basaltic-andesite (53% SiO2) to quartz latite (67% SiO2). The precaldera intermediate-composition lavas have anomalously high Ni and MgO contents and reversely zoned hornblende and augite phenocrysts, indicating mixing between primitive basalts and fractionated magmas. Isotopic data indicate that all of the intermediate-composition rocks studied contain large crustal components, although xenocrysts are found only in one unit. Inception of alkaline magmatism (alkalic dacite to high-SiO2 peralkaline rhyolite) correlates with, initiation of regional extension approximately 26 Ma ago. The Questa caldera formed 26.5 Ma ago upon eruption of the >500 km3 high-SiO2 peralkaline Amalia Tuff. Phenocryst compositions preserved in the cogenetic peralkaline granite suggest that the Amalia Tuff magma initially formed from a trace element-enriched, high-alkali metaluminous magma; isotopic data suggest that the parental magmas contain a large crustal component. Degassing of water- and halogen-rich alkali basalts may have provided sufficient volatile transport of alkalis and other elements into the overlying silicic magma chamber to drive the Amalia Tuff magma to peralkaline compositions. Trace element variations within the Amalia Tuff itself may be explained solely by 75% crystal fractionation of the observed phenocrysts. Crystal settling, however, is inconsistent with mineralogical variations in the tuff, and crystallization is thought to have occurred at a level below that tapped by the eruption. Spatially associated Miocene (15-11 Ma) lavas did not assimilate large amounts of crust or mix with primitive basaltic magmas. Both mixing and crustal assimilation processes appear to require development of relatively large magma chambers in the crust that are sustained by large basalt fluxes from the mantle. The lack of extensive crustal contamination and mixing in the Miocene lavas may be related to a decreased basalt flux or initiation of blockfaulting that prevented pooling of basaltic magma in the crust. ?? 1988 Springer-Verlag.

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.

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

Evaluation of modified crystal violet chromoendoscopy procedure using new mucosal pit pattern classification for detection of Barrett's dysplastic lesions.

PubMed

Yuki, T; Amano, Y; Kushiyama, Y; Takahashi, Y; Ose, T; Moriyama, I; Fukuhara, H; Ishimura, N; Koshino, K; Furuta, K; Ishihara, S; Adachi, K; Kinoshita, Y

2006-05-01

Pit pattern diagnosis is important for endoscopic detection of dysplastic Barrett's lesions, though using magnification endoscopy can be difficult and laborious. We investigated the usefulness of a modified crystal violet chromoendoscopy procedure and utilised a new pit pattern classification for diagnosis of dysplastic Barrett's lesions. A total of 1,030 patients suspected of having a columnar lined oesophagus were examined, of whom 816 demonstrated a crystal violet-stained columnar lined oesophagus. The early group of patients underwent 0.05% crystal violet chromoendoscopy, while the later group was examined using 0.03% crystal violet with 3.0% acetate. A targeted biopsy of the columnar lined oesophagus was performed using crystal violet staining after making a diagnosis of closed or open type pit pattern with a newly proposed system of classification. The relationship between type of pit pattern and histologically identified dysplastic Barrett's lesions was evaluated. Dysplastic Barrett's lesions were identified in biopsy samples with an open type pit pattern with a sensitivity of 96.0%. Further, Barrett's mucosa with the intestinal predominant mucin phenotype was closely associated with the open type pit pattern (sensitivity 81.9%, specificity 95.6%). The new pit pattern classification for diagnosis of Barrett's mucosa was found to be useful for identification of cases with dysplastic lesions and possible malignant potential using a crystal violet chromoendoscopic procedure.

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.

Synergistic Utility of Brain Natriuretic Peptide and Left Ventricular Global Longitudinal Strain in Asymptomatic Patients With Significant Primary Mitral Regurgitation and Preserved Systolic Function Undergoing Mitral Valve Surgery.

PubMed

Alashi, Alaa; Mentias, Amgad; Patel, Krishna; Gillinov, A Marc; Sabik, Joseph F; Popović, Zoran B; Mihaljevic, Tomislav; Suri, Rakesh M; Rodriguez, L Leonardo; Svensson, Lars G; Griffin, Brian P; Desai, Milind Y

2016-07-01

In asymptomatic patients with ≥3+ mitral regurgitation and preserved left ventricular (LV) ejection fraction who underwent mitral valve surgery, we sought to discover whether baseline LV global longitudinal strain (LV-GLS) and brain natriuretic peptide provided incremental prognostic utility. Four hundred and forty-eight asymptomatic patients (61±12 years and 69% men) with ≥3+ primary mitral regurgitation and preserved left ventricular ejection fraction, who underwent mitral valve surgery (92% repair) at our center between 2005 and 2008, were studied. Baseline clinical and echocardiographic data (including LV-GLS using Velocity Vector Imaging, Siemens, PA) were recorded. The Society of Thoracic Surgeons score was calculated. The primary outcome was death. Mean Society of Thoracic Surgeons score, left ventricular ejection fraction, mitral effective regurgitant orifice, indexed LV end-diastolic volume, and right ventricular systolic pressure were 4±1%, 62±3%, 0.55±0.2 cm(2), 58±13 cc/m(2), and 37±15 mm Hg, respectively. Forty-five percent of patients had flail. Median log-transformed BNP and LV-GLS were 4.04 (absolute brain natriuretic peptide: 60 pg/dL) and -20.7%. At 7.7±2 years, death occurred in 41 patients (9%; 0% at 30 days). On Cox analysis, a higher Society of Thoracic Surgeons score (hazard ratio 1.55), higher baseline right ventricular systolic pressure (hazard ratio 1.11), more abnormal LV-GLS (hazard ratio 1.17), and higher median log-transformed BNP (hazard ratio 2.26) were associated with worse longer-term survival (all P<0.01). Addition of LV-GLS and median log-transformed BNP to a clinical model (Society of Thoracic Surgeons score and baseline right ventricular systolic pressure) provided incremental prognostic utility (χ(2) for longer-term mortality increased from 31-47 to 61; P<0.001). In asymptomatic patients with significant primary mitral regurgitation and preserved left ventricular ejection fraction who underwent mitral valve surgery, brain natriuretic peptide and LV-GLS provided synergistic risk stratification, independent of established factors. © 2016 American Heart Association, Inc.

Orientation dependence of the stress rupture properties of Nickel-base superalloy single crystals

NASA Technical Reports Server (NTRS)

Mackay, R. A.

1981-01-01

The influence of orientation of the stress rupture behavior of Mar-M247 single crystals was studied. Stress rupture tests were performed at 724 MPa and 774 C where the effect of anisotropy is prominent. The mechanical behavior of the single crystals was rationalized on the basis of the Schmid factors for the operative slip systems and the lattice rotations which the crystals underwent during deformation. The stress rupture lives were found to be greatly influenced by the lattice rotations required to produce intersecting slip, because steady-state creep does not begin until after the onset of intersecting slip. Crystals which required large rotations to become oriented for intersecting slip exhibited a large primary creep strain, a large effective stress level at the onset of steady-state creep, and consequently a short stress rupture life. A unified analysis was attained for the stress rupture behavior of the Mar-M247 single crystals tested in this study at 774 C and that of the Mar-M200 single crystals tested in a prior study at 760 C. In this analysis, the standard 001-011-111 stereographic triangle was divided into several regions of crystallographic orientation which were rank ordered according to stress rupture life for this temperature regime. This plot indicates that those crystals having orientations within about 25 deg of the 001 exhibited significantly longer lives when their orientations were closer to the 001-011 boundary of the stereographic triangle than to the 001-111 boundary.

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).

Left ventricular systolic dysfunction after transcatheter closure of a large patent ductus arteriosus.

PubMed

Galal, Mohammed Omar; Arfi, Muhammed Amin; Nicole, Sekarski; Payot, Maurice; Hussain, Arif; Qureshi, Shakeel

2005-11-01

A 12-year-old boy reported in outpatient department with history of shortness of breath and dyspnoea on moderate exertion. Physical examination was significant for bounding pulses and for a continuous murmur III/VI, best heard at the left upper sternal border. Echocardiography confirmed a large patent arterial duct with shortening fraction of 33%. He underwent successful transcatheter closure of the patent arterial, using Amplatzer duct occluder 12/10. Few hours later echocardiography revealed an unexpected, yet important depression of left ventricular systolic function with shortening fraction decreasing to 24% and then two weeks later decreasing further to 20%. At a follow-up after four months, he had improved clinically but left ventricular dysfunction still persisted with shortening fraction of 24%.

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.

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.

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.

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.

Definitive fractionated re-irradiation for local recurrence following stereotactic body radiotherapy for primary lung cancer.

PubMed

Yoshitake, Tadamasa; Shioyama, Yoshiyuki; Nakamura, Katsumasa; Sasaki, Tomonari; Ohga, Saiji; Shinoto, Makoto; Terashima, Kotaro; Asai, Kaori; Matsumoto, Keiji; Hirata, Hideki; Honda, Hiroshi

2013-12-01

To retrospectively evaluate the efficacy and safety of definitive fractionated re-irradiation for local recurrence following stereotactic body radiotherapy (SBRT) for primary lung cancer. Between April 2003 and December 2011, 398 patients with primary lung tumor underwent SBRT at the Kyushu University Hospital, and 46 out of these developed local recurrence after SBRT. Definitive fractionated re-irradiation was performed for 17 out of the 46 patients. The median dose of re-irradiation was 60 Gy/ 30 fractions. Concurrent chemotherapy was given to four patients. The median follow-up duration was 12.6 months. At one year post-re-irradiation, local progression-free survival was 33.8%; progression-free survival, 30.9%; cause-specific survival, 79.3%; and overall survival, 74.7%. No severe adverse events were observed during the follow-up. Definitive fractionated re-irradiation is thought to be a safe alternative therapy for local recurrence following SBRT, although its efficacy may be not entirely satisfactory.

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

Carbohydrates and amino compounds as short-term indicators of soil management

USDA-ARS?s Scientific Manuscript database

The objective of this study was to investigate the changes in labile soil organic matter (SOM) fractions during the transition from conventional to organic farming. Two field experiments underwent the transition from conventional to organic farming during 2009–2011 in the south of Italy, at Foggia (...

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.

Sevelamer crystals in the mucosa of the gastrointestinal tract in a teenager with end-stage renal disease.

PubMed

Kim, Joseph; Olson, Kristin; Butani, Lavjay

2016-02-01

Non-calcium-containing phosphate binders, such as sevelamer preparations, are being increasingly used in patients on dialysis due to their lower association with hypercalcemia and cardiovascular morbidity and mortality. While minor gastrointestinal side effects are quite common with the use of sevelamer, more serious gastrointestinal toxicities have only rarely been reported. We report a pediatric patient on maintenance dialysis receiving sevelamer hydrochloride who developed severe abdominal pain and a high-grade stricture of the sigmoid colon. The patient underwent exploratory laparotomy, resulting in a partial colectomy and colostomy. Histopathologic examination showed colonic mucosal injury and characteristic "fish-scale"-like sevelamer hydrochloride crystals within the mucosa. Whether the sevelamer crystals were causal, contributory or purely incidental remains to be clearly elucidated. However, our case raises sufficient concern to warrant additional investigation into whether there is a causal relationship between sevelamer use and intestinal mucosal injury.

A liquid-liquid transition in supercooled aqueous solution related to the HDA-LDA transition

NASA Astrophysics Data System (ADS)

Woutersen, Sander; Ensing, Bernd; Hilbers, Michiel; Zhao, Zuofeng; Angell, C. Austen

2018-03-01

Simulations and theory suggest that the thermodynamic anomalies of water may be related to a phase transition between two supercooled liquid states, but so far this phase transition has not been observed experimentally because of preemptive ice crystallization. We used calorimetry, infrared spectroscopy, and molecular dynamics simulations to investigate a water-rich hydrazinium trifluoroacetate solution in which the local hydrogen bond structure surrounding a water molecule resembles that in neat water at elevated pressure, but which does not crystallize upon cooling. Instead, this solution underwent a sharp, reversible phase transition between two homogeneous liquid states. The hydrogen-bond structures of these two states are similar to those established for high- and low-density amorphous (HDA and LDA) water. Such structural similarity supports theories that predict a similar sharp transition in pure water under pressure if ice crystallization could be suppressed.

Transepidermal drug delivery: a new treatment option for areata alopecia?

PubMed

Issa, Maria Claudia Almeida; Pires, Marianna; Silveira, Priscilla; Xavier de Brito, Esther; Sasajima, Cristiane

2015-02-01

Transepidermal drug delivery (TED) is a new potential method in dermatology. Permeability alterations induced by ablative fractional resurfacing have been described with the aim to increasing the delivery of different substances into the skin. To evaluate clinical response and side effects of TED in areata alopecia (AA) treatment using ablative fractional methods associated with acoustic pressure ultrasound (US) to deliver triamcinolone solution into the skin. Five cases of AA underwent treatment which comprised of 3 steps: 1) Ablative fractioned RF or CO2 laser 2) topical application of triamcinolone 3) acoustic pressure wave US. The number of sessions varied according to the clinical response, ranging from one to six sessions. All patients had complete recovery of the area treated. Two of them treated with ablative fractional RF + triamcinolone + US had complete response after three and six sessions. The other two treated with ablative fractional CO2 + triamcinolone + US had complete response after one session. Fractioned ablative resurfacing associated with acoustic pressure wave US is a new option to areata alopecia treatment with good clinical result and low incidence of side effects.

Molecular effects of fractional carbon dioxide laser resurfacing on photodamaged human skin.

PubMed

Reilly, Michael J; Cohen, Marc; Hokugo, Akishige; Keller, Gregory S

2010-01-01

Objective To elucidate the sequential changes in protein expression that play a role in the clinically beneficial results seen with fractional carbon dioxide (CO(2)) laser resurfacing of the face and neck. Methods Nine healthy volunteers were recruited for participation from the senior author's facial plastic surgery practice. After informed consent was obtained, each volunteer underwent a 2-mm punch biopsy from a discrete area of infra-auricular neck skin prior to laser treatment. Patients then immediately underwent laser resurfacing of photodamaged face and neck skin at a minimal dose (30 W for 0.1 second) with the Pixel Perfect fractional CO(2) laser. On completion of the treatment, another biopsy specimen was taken adjacent to the first site. Additional biopsy specimens were subsequently taken from adjacent skin at 2 of 3 time points (day 7, day 14, or day 21). RNA was extracted from the specimens, and reverse transcriptase-polymerase chain reaction and protein microarray analysis were performed. Comparisons were then made between time points using pairwise comparison testing. Results We found statistically significant changes in the gene expression of several matrix metalloproteinases (MMPs). The data demonstrate a consistent up-regulation of MMPs 1, 3, 9, and 13, all of which have been previously reported for fully ablative CO(2) laser resurfacing. There was also a statistically significant increase in MMP-10 and MMP-11 levels in this data set. Conclusion This study suggests that the molecular mechanisms of action are similar for both fractional and fully ablative CO(2) laser resurfacing.

Prevalence of monosodium urate deposits in a population of rheumatoid arthritis patients with hyperuricemia.

PubMed

Petsch, Christina; Araujo, Elizabeth G; Englbrecht, Matthias; Bayat, Sara; Cavallaro, Alexander; Hueber, Axel J; Lell, Michael; Schett, Georg; Manger, Bernhard; Rech, Juergen

2016-06-01

To investigate the prevalence of monosodium urate (MSU) crystal deposits, indicative for gout, in a population of rheumatoid arthritis (RA) patients with concomitant hyperuricemia and to analyze the clinical and disease-specific characteristics of RA patients who exhibit MSU crystal deposits. Overall, 100 consecutive patients with the diagnosis of RA and a serum urate level above 6mg/dl underwent dual energy computed tomography (DECT) of both feet and hands to search for MSU crystals in a prospective study between October 2011 and July 2013. Presence and extent of MSU crystal deposits on DECT was assessed by automated volume measurement. Demographic and disease-specific characteristics were recorded and included into two logistic regression models to test for the factors associated with MSU crystal deposits in RA. Hyperuricemic RA patients were mostly male (55%), over 60 years of age (63 ± 11 years), had established disease (8.7 ± 10.5 years) and a mean disease activity score 28 (DAS 28) of 3.2. In total, 20 out of 100 patients displayed MSU crystal deposits in DECT. Interestingly, the majority (70%) of the RA patients positive for MSU crystal deposits were seronegative RA patients. Hence, every third seronegative RA patient had MSU crystal deposits. According to logistic regression model analysis, seronegative status correlated positively with presence of urate deposits (p = 0.019). These data show that a considerable number of RA patients display periarticular MSU crystal deposits. Seronegative patients were shown to be predominantly affected with every third patient being positive for urate deposits. Copyright © 2016 Elsevier Inc. All rights reserved.

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.

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.

Shear-induced structural transitions in Newtonian non-Newtonian two-phase flow

NASA Astrophysics Data System (ADS)

Cristobal, G.; Rouch, J.; Colin, A.; Panizza, P.

2000-09-01

We show the existence under shear flow of steady states in a two-phase region of a brine-surfactant system in which lyotropic dilute lamellar (non-Newtonian) and sponge (Newtonian) phases are coexisting. At high shear rates and low sponge phase-volume fractions, we report on the existence of a dynamic transition corresponding to the formation of a colloidal crystal of multilamellar vesicles (or ``onions'') immersed in the sponge matrix. As the sponge phase-volume fraction increases, this transition exhibits a hysteresis loop leading to a structural bistability of the two-phase flow. Contrary to single phase lamellar systems where it is always 100%, the onion volume fraction can be monitored continuously from 0 to 100 %.

Micromechanical models for the stiffness and strength of UHMWPE macrofibrils

NASA Astrophysics Data System (ADS)

Dong, Hai; Wang, Zheliang; O'Connor, Thomas C.; Azoug, Aurelie; Robbins, Mark O.; Nguyen, Thao D.

2018-07-01

Ultrahigh molecular weight polyethylene (UHMWPE) fibers have a complex hierarchical structure that at the micron-scale is composed of oriented chain crystals, lamellar crystals, and amorphous domains organized into macrofibrils. We developed a computational micromechanical modeling study of the effects of the morphological structure and constituent material properties on the deformation mechanisms, stiffness and strength of the UHMWPE macrofibrils. Specifically, we developed four representative volume elements, which differed in the arrangement and orientation of the lamellar crystals, to describe the various macrofibrillar microstructures observed in recent experiments. The stiffness and strength of the crystals were determined from molecular dynamic simulations of a pure PE crystal. A finite deformation crystal plasticity model was used to describe the crystals and an isotropic viscoplastic model was used for the amorphous phase. The results show that yielding in UHMWPE macrofibrils under axial tension is dominated by the slip in the oriented crystals, while yielding under transverse compression and shear is dominated by slips in both the oriented and lamellar crystals. The results also show that the axial modulus and strength are mainly determined by the volume fraction of the oriented crystals and are insensitive to the arrangements of the lamellar crystals when the modulus of the amorphous phase is significantly smaller than that of the crystals. In contrast, the arrangement and size of the lamellar crystals have a significant effect on the stiffness and strength under transverse compression and shear. These findings can provide a guide for new materials and processing design to improve the properties of UHMWPE fibers by controlling the macrofibrillar morphologies.

Applying the X-ray diffraction analysis for estimating the height and width of nanorods in low symmetry crystal multiphase materials

NASA Astrophysics Data System (ADS)

Mokhtari, Ali; Soleimanian, Vishtasb; Dehkordi, Hamed Aleebrahim; Dastafkan, Kamran

2017-11-01

In this work the potential of Rietveld refinement procedure is used to study the shape and size of non-spherical nanocrystallites. The main advantages of this approach are that not only it can successfully extend to all nanomaterials with different crystal symmetries but also it can evaluate the various phases of multiple materials comparing to electron microscopy methods. Therefore, between seven crystal systems, the formulation of monoclinic and hexagonal crystals is developed. This procedure is applied for the mixture of sodium carbonate and zinc oxide nanocrystallites at different fractions of doped gadolinium oxide. It is found that the crystallites of sodium carbonate and zinc oxide have the rod and ellipsoidal shapes, respectively. The microstructure results are compared with the results of scanning electron microscopy imaging. Good agreement is achieved between the results of scanning electron microscopy and Rietveld methods.

Zinc Sulphide Overlayer Two-Dimensional Photonic Crystal for Enhanced Extraction of Light from a Micro Cavity Light-Emitting Diode

NASA Astrophysics Data System (ADS)

Mastro, Michael A.; Kim, Chul Soo; Kim, Mijin; Caldwell, Josh; Holm, Ron T.; Vurgaftman, Igor; Kim, Jihyun; Eddy, Charles R., Jr.; Meyer, Jerry R.

2008-10-01

A two-dimensional (2D) ZnS photonic crystal was deposited on the surface of a one-dimensional (1D) III-nitride micro cavity light-emitting diode (LED), to intermix the light extraction features of both structures (1D+2D). The deposition of an ideal micro-cavity optical thickness of ≈λ/2 is impractical for III-nitride LEDs, and in realistic multi-mode devices a large fraction of the light is lost to internal refraction as guided light. Therefore, a 2D photonic crystal on the surface of the LED was used to diffract and thus redirect this guided light out of the semiconductor over several hundred microns. Additionally, the employment of a post-epitaxy ZnS 2D photonic crystal avoided the typical etching into the GaN:Mg contact layer, a procedure which can cause damage to the near surface.

Survey and analysis of crystal polymorphism in organic structures

PubMed Central

Kaur, Ramanpreet

2018-01-01

With the intention of producing the most comprehensive treatment of the prevalence of crystal polymorphism among structurally characterized materials, all polymorphic compounds flagged as such within the Cambridge Structural Database (CSD) are analysed and a list of crystallographically characterized organic polymorphic compounds is assembled. Classifying these structures into subclasses of anhydrates, salts, hydrates, non-hydrated solvates and cocrystals reveals that there are significant variations in polymorphism prevalence as a function of crystal type, a fact which has not previously been recognized in the literature. It is also shown that, as a percentage, polymorphic entries are decreasing temporally within the CSD, with the notable exception of cocrystals, which continue to rise at a rate that is a constant fraction of the overall entries. Some phenomena identified that require additional scrutiny include the relative prevalence of temperature-induced phase transitions among organic salts and the paucity of polymorphism in crystals with three or more chemical components. PMID:29765601

Crystal habit-tuned nanoplate material of Li[Li1/3-2x/3NixMn2/3-x/3]O₂ for high-rate performance lithium-ion batteries.

PubMed

Wei, Guo-Zhen; Lu, Xia; Ke, Fu-Sheng; Huang, Ling; Li, Jun-Tao; Wang, Zhao-Xiang; Zhou, Zhi-You; Sun, Shi-Gang

2010-10-15

A cathode for high-rate performance lithium-ion batteries (LIBs) has been developed from a crystal habit-tuned nanoplate Li(Li(0.17)Ni(0.25)Mn(0.58))O₂ material, in which the proportion of (010) nanoplates (see figure) has been significantly increased. The results demonstrate that the fraction of the surface that is electrochemically active for Li(+) transportation is a key criterion for evaluating the different nanostructures of potential LIB materials.

Transport and magnetic properties of HITPERM alloys

NASA Astrophysics Data System (ADS)

Pekala, K.; Latuch, J.; Pekala, M.; Skorvanek, I.; Jaskiewicz, P.

2003-02-01

Nanocrystalline HITPERM alloys Fe44.6Co43.3X7.4B3.7Cu1 (X = Nb, Zr, Hf) prepared by crystallization of amorphous precursors are studied by magnetization and electrical resistivity measurements for the first time. Structural and magnetic components of the electrical resistivity are separated. The electrical resistivity of the nanocrystalline α' (FeCo) phase calculated using the Maxwell Garnett relation proves strong electron scattering on the grain boundaries. The temperature variation of the crystalline fraction during the first crystallization stage is calculated for the Hf based alloy.

In situ neutron diffraction study of twin reorientation and pseudoplastic strain in Ni-Mn-Ga single crystals

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

Stoica, Alexandru Dan

2011-01-01

Twin variant reorientation in single-crystal Ni-Mn-Ga during quasi-static mechanical compression was studied using in situ neutron diffraction. The volume fraction of reoriented twin variants for different stress amplitudes were obtained from the changes in integrated intensities of high-order neutron diffraction peaks. It is shown that, during compressive loading, {approx}85% of the twins were reoriented parallel to the loading direction resulting in a maximum pseudoplasticstrain of {approx}5.5%, which is in agreement with measured macroscopic strain.

Twin-variant reorientation strain in Ni-Mn-Ga single crystal during quasi-static mechanical compression

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

Pramanick, Abhijit; An, Ke; Stoica, Alexandru Dan

2011-01-01

Twin variant reorientation in single crystal Ni-Mn-Ga during quasi-static mechanical compression was studied using in-situ neutron diffraction. The volume fraction of reoriented twin variants for different stress amplitudes were obtained from the changes in integrated intensities of high-order neutron diffraction peaks. It is shown that during compressive loading, ~85% of the twins were reoriented parallel to the loading direction resulting in a maximum macroscopic strain of ~5.5%, which is in agreement with measured macroscopic strain.

Crystal structure and superconducting properties of KSr2Nb3O10

NASA Astrophysics Data System (ADS)

Kawaguchi, T.; Horigane, K.; Itoh, Y.; Kobayashi, K.; Horie, R.; Kambe, T.; Akimitsu, J.

2018-05-01

We performed X-ray diffraction (XRD) and DC magnetic susceptibility measurements to elucidate the crystal structure and superconducting properties of KSr2Nb3O10. From the diffraction pattern indexing, it was found that KSr2Nb3O10 crystallizes with monoclinic symmetry, space group P21/m(11). We succeeded in preparing high temperature (HT) and low temperature (LT) phases of KSr2Nb3O10 powder samples synthesized by a conventional solid state reaction and an ion-exchange reaction, respectively. Superconductivity was observed at 4 K by Li intercalation and it was found that the superconducting volume fraction of the LT phase ( 1.4%) is clearly larger than that of the HT phase (0.07%).

One Crystal, Two Temperatures: Cryocooling Penalties Alter Ligand Binding to Transient Protein Sites

DOE PAGES

Fischer, Marcus; Shoichet, Brian K.; Fraser, James S.

2015-05-28

Interrogating fragment libraries by X-ray crystallography is a powerful strategy for discovering allosteric ligands for protein targets. Cryocooling of crystals should theoretically increase the fraction of occupied binding sites and decrease radiation damage. However, it might also perturb protein conformations that can be accessed at room temperature. Using data from crystals measured consecutively at room temperature and at cryogenic temperature, we found that transient binding sites could be abolished at the cryogenic temperatures employed by standard approaches. Finally, changing the temperature at which the crystallographic data was collected could provide a deliberate perturbation to the equilibrium of protein conformations andmore » help to visualize hidden sites with great potential to allosterically modulate protein function.« less

Surface topography and crystal and domain structures of films of ferroelectric copolymer of vinylidene difluoride and trifluoroethylene

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

Kochervinskii, V. V., E-mail: kochval@mail.ru; Kiselev, D. A.; Malinkovich, M. D.

2017-03-15

The crystallization of a copolymer from a solution at room temperature is found to lead to the formation of a metastable structure, characterized by the coexistence of ferroelectric and paraelectric phases. The fraction of the latter decreases after annealing above the Curie point. Atomic force microscopy (AFM) has revealed a difference in the surface topographies between the films contacting with air and the films contacting with a glass substrate. The microstructure of copolymer chains has been investigated by {sup 19}F NMR spectroscopy. The chain fragments with “defect” attached monomeric units are ejected to the surface. The character of the ferroelectricmore » domains formed during crystallization and their size distribution are analyzed.« less

Surface heat shock protein 90 serves as a potential receptor for calcium oxalate crystal on apical membrane of renal tubular epithelial cells.

PubMed

Fong-Ngern, Kedsarin; Sueksakit, Kanyarat; Thongboonkerd, Visith

2016-07-01

Adhesion of calcium oxalate monohydrate (COM) crystals on renal tubular epithelial cells is a crucial step in kidney stone formation. Finding potential crystal receptors on the apical membrane of the cells may lead to a novel approach to prevent kidney stone disease. Our previous study identified a large number of crystal-binding proteins on the apical membrane of MDCK cells. However, their functional role as potential crystal receptors had not been validated. The present study aimed to address the potential role of heat shock protein 90 (HSP90) as a COM crystal receptor. The apical membrane was isolated from polarized MDCK cells by the peeling method and recovered proteins were incubated with COM crystals. Western blot analysis confirmed the presence of HSP90 in the apical membrane and the crystal-bound fraction. Immunofluorescence staining without permeabilization and laser-scanning confocal microscopy confirmed the surface HSP90 expression on the apical membrane of the intact cells. Crystal adhesion assay showed that blocking surface HSP90 by specific anti-HSP90 antibody and knockdown of HSP90 by small interfering RNA (siRNA) dramatically reduced crystal binding on the apical surface of MDCK cells (by approximately 1/2 and 2/3, respectively). Additionally, crystal internalization assay revealed the presence of HSP90 on the membrane of endocytic vesicle containing the internalized COM crystal. Moreover, pretreatment of MDCK cells with anti-HSP90 antibody significantly reduced crystal internalization (by approximately 1/3). Taken together, our data indicate that HSP90 serves as a potential receptor for COM crystals on the apical membrane of renal tubular epithelial cells and is involved in endocytosis/internalization of the crystals into the cells.

Do protein crystals nucleate within dense liquid clusters?

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

Maes, Dominique, E-mail: dommaes@vub.ac.be; Vorontsova, Maria A.; Potenza, Marco A. C.

2015-06-27

The evolution of protein-rich clusters and nucleating crystals were characterized by dynamic light scattering (DLS), confocal depolarized dynamic light scattering (cDDLS) and depolarized oblique illumination dark-field microscopy. Newly nucleated crystals within protein-rich clusters were detected directly. These observations indicate that the protein-rich clusters are locations for crystal nucleation. Protein-dense liquid clusters are regions of high protein concentration that have been observed in solutions of several proteins. The typical cluster size varies from several tens to several hundreds of nanometres and their volume fraction remains below 10{sup −3} of the solution. According to the two-step mechanism of nucleation, the protein-rich clustersmore » serve as locations for and precursors to the nucleation of protein crystals. While the two-step mechanism explained several unusual features of protein crystal nucleation kinetics, a direct observation of its validity for protein crystals has been lacking. Here, two independent observations of crystal nucleation with the proteins lysozyme and glucose isomerase are discussed. Firstly, the evolutions of the protein-rich clusters and nucleating crystals were characterized simultaneously by dynamic light scattering (DLS) and confocal depolarized dynamic light scattering (cDDLS), respectively. It is demonstrated that protein crystals appear following a significant delay after cluster formation. The cDDLS correlation functions follow a Gaussian decay, indicative of nondiffusive motion. A possible explanation is that the crystals are contained inside large clusters and are driven by the elasticity of the cluster surface. Secondly, depolarized oblique illumination dark-field microscopy reveals the evolution from liquid clusters without crystals to newly nucleated crystals contained in the clusters to grown crystals freely diffusing in the solution. Collectively, the observations indicate that the protein-rich clusters in lysozyme and glucose isomerase solutions are locations for crystal nucleation.« less

Scavenging of black carbon in mixed phase clouds at the high alpine site Jungfraujoch

NASA Astrophysics Data System (ADS)

Cozic, J.; Verheggen, B.; Mertes, S.; Connolly, P.; Bower, K.; Petzold, A.; Baltensperger, U.; Weingartner, E.

2007-04-01

The scavenging of black carbon (BC) in liquid and mixed phase clouds was investigated during intensive experiments in winter 2004, summer 2004 and winter 2005 at the high alpine research station Jungfraujoch (3580 m a.s.l., Switzerland). Aerosol residuals were sampled behind two well characterized inlets; a total inlet which collected cloud particles (droplets and ice particles) as well as interstitial (unactivated) aerosol particles; an interstitial inlet which collected only interstitial aerosol particles. BC concentrations were measured behind each of these inlets along with the submicrometer aerosol number size distribution, from which a volume concentration was derived. These measurements were complemented by in-situ measurements of cloud microphysical parameters. BC was found to be scavenged into the condensed phase to the same extent as the bulk aerosol, which suggests that BC was covered with soluble material through aging processes, rendering it more hygroscopic. The scavenged fraction of BC (FScav,BC), defined as the fraction of BC that is incorporated into cloud droplets and ice crystals, decreases with increasing cloud ice mass fraction (IMF) from FScav,BC=60% in liquid phase clouds to FScav,BC~5-10% in mixed-phase clouds with IMF>0.2. This can be explained by the evaporation of liquid droplets in the presence of ice crystals (Wegener-Bergeron-Findeisen process), releasing BC containing cloud condensation nuclei back into the interstitial phase. In liquid clouds, the scavenged BC fraction is found to decrease with decreasing cloud liquid water content. The scavenged BC fraction is also found to decrease with increasing BC mass concentration since there is an increased competition for the available water vapour.

Scavenging of black carbon in mixed phase clouds at the high alpine site Jungfraujoch

NASA Astrophysics Data System (ADS)

Cozic, J.; Verheggen, B.; Mertes, S.; Connolly, P.; Bower, K.; Petzold, A.; Baltensperger, U.; Weingartner, E.

2006-11-01

The scavenging of black carbon (BC) in liquid and mixed phase clouds was investigated during intensive experiments in winter 2004, summer 2004 and winter 2005 at the high alpine research station Jungfraujoch (3580 m a.s.l., Switzerland). Aerosol residuals were sampled behind two well characterized inlets; a total inlet which collected cloud particles (drops and ice particles) as well as interstitial aerosol particles; an interstitial inlet which collected only interstitial (unactivated) aerosol particles. BC concentrations were measured behind each of these inlets along with the submicrometer aerosol number size distribution, from which a volume concentration was derived. These measurements were complemented by in-situ measurements of cloud microphysical parameters. BC was found to be scavenged into the cloud phase to the same extent as the bulk aerosol, which suggests that BC was covered with soluble material through aging processes, rendering it more hygroscopic. The scavenged fraction of BC (FScav,BC), defined as the fraction of BC that is incorporated into cloud droplets and ice crystals, decreases with increasing cloud ice mass fraction (IMF) from FScav,BC=60% in liquid phase clouds to FScav,BC~10% in mixed-phase clouds with IMF>0.2. This is explained by the evaporation of liquid droplets in the presence of ice crystals (Wegener-Bergeron-Findeisen process), releasing BC containing cloud condensation nuclei back into the interstitial phase. In liquid clouds, the scavenged BC fraction is found to decrease with decreasing cloud liquid water content. The scavenged BC fraction is also found to decrease with increasing BC mass concentration since there is an increased competition for the available water vapour.

Origin of heavy Fe isotope compositions in high-silica igneous rocks: A rhyolite perspective

NASA Astrophysics Data System (ADS)

Du, De-Hong; Wang, Xiao-Lei; Yang, Tao; Chen, Xin; Li, Jun-Yong; Li, Weiqiang

2017-12-01

The origin of heavy Fe isotope compositions in high-silica (>70 wt% SiO2) igneous rocks remains a highly controversial topic. Considering that fluid exsolution in eruptive rocks is more straight-forward to constrain than in plutonic rocks, this study addresses the problem of Fe isotope fractionation in high-silica igneous rocks by measuring Fe isotope compositions of representative rhyolitic samples from the Neoproterozoic volcanic-sedimentary basins in southern China and the Triassic Tu Le Basin in northern Vietnam. The samples show remarkably varied δ56FeIRMM014 values ranging from 0.05 ± 0.05‰ to 0.55 ± 0.05‰, which is among the highest values reported from felsic rocks. The extensional tectonic setting and short melt residence time in magma chambers for the studied rhyolites rule out Soret diffusion and thermal migration processes as causes of the high δ56Fe values. Effects of volcanic degassing and fluid exsolution on bulk rock δ56Fe values for the rhyolites are also assessed using bulk rock geochemical indicators and Rayleigh fractionation models, and these processes are found to be insufficient to produce resolvable changes in Fe isotope compositions of the residual melt. The most probable mechanism accounting for heavy Fe isotope compositions in the high-silica rhyolites is narrowed down to fractional crystallization processes in the magma before rhyolite eruption. Removal of isotopically light Fe-bearing minerals (i.e. ulvöspinel-rich titanomagnetite, ilmenite and biotite) is proposed as the main cause of Fe isotope variation in silicic melts during magmatic evolution. This study implies that crystal fractionation is the dominant mechanism that controls Fe isotope fractionation in eruptive rocks and Fe isotopes could be used to study magmatic differentiation of high-silica magmas.

Febuxostat for the Prevention of Recurrent 2,8-dihydroxyadenine Nephropathy due to Adenine Phosphoribosyltransferase Deficiency Following Kidney Transplantation.

PubMed

Nanmoku, Koji; Kurosawa, Akira; Shinzato, Takahiro; Shimizu, Toshihiro; Kimura, Takaaki; Yagisawa, Takashi

2017-01-01

Adenine phosphoribosyltransferase (APRT) deficiency is a rare autosomal recessive disorder that results in irreversible renal damage due to 2,8-dihydroxyadenine (DHA) nephropathy. A 28-year-old man underwent living-related kidney transplantation for chronic kidney disease of unknown etiology. Numerous spherical brownish crystals observed in his urinary sediment on postoperative day 3 and were observed within the tubular lumen of renal allograft biopsy specimens on postoperative day 7. After a genetic diagnosis, febuxostat treatment was started on postoperative day 7, with the dosage gradually increased to 80 mg/day until complete the disappearance of 2,8-DHA crystals. Febuxostat prevented secondary 2,8-DHA nephropathy after kidney transplantation.

A pseudo-tetragonal tungsten bronze superstructure: a combined solution of the crystal structure of K6.4(Nb,Ta)(36.3)O94 with advanced transmission electron microscopy and neutron diffraction.

PubMed

Paria Sena, Robert; Babaryk, Artem A; Khainakov, Sergiy; Garcia-Granda, Santiago; Slobodyanik, Nikolay S; Van Tendeloo, Gustaaf; Abakumov, Artem M; Hadermann, Joke

2016-01-21

The crystal structure of the K6.4Nb28.2Ta8.1O94 pseudo-tetragonal tungsten bronze-type oxide was determined using a combination of X-ray powder diffraction, neutron diffraction and transmission electron microscopy techniques, including electron diffraction, high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), annular bright field STEM (ABF-STEM) and energy-dispersive X-ray compositional mapping (STEM-EDX). The compound crystallizes in the space group Pbam with unit cell parameters a = 37.468(9) Å, b = 12.493(3) Å, c = 3.95333(15) Å. The structure consists of corner sharing (Nb,Ta)O6 octahedra forming trigonal, tetragonal and pentagonal tunnels. All tetragonal tunnels are occupied by K(+) ions, while 1/3 of the pentagonal tunnels are preferentially occupied by Nb(5+)/Ta(5+) and 2/3 are occupied by K(+) in a regular pattern. A fractional substitution of K(+) in the pentagonal tunnels by Nb(5+)/Ta(5+) is suggested by the analysis of the HAADF-STEM images. In contrast to similar structures, such as K2Nb8O21, also parts of the trigonal tunnels are fractionally occupied by K(+) cations.

Fabrication and Evaluation of Bis-GMA/TEGDMA Dental Resins/Composites Containing Nano Fibrillar Silicate

PubMed Central

Tian, Ming; Gao, Yi; Liu, Yi; Liao, Yiliang; Hedin, Nyle E.; Fong, Hao

2008-01-01

Objective To investigate the reinforcement of Bis-GMA/TEGDMA dental resins (without conventional glass filler) and composites (with conventional glass filler) with various mass fractions of nano fibrillar silicate (FS). Methods Three dispersion methods were studied to separate the silanized FS as nano-scaled single crystals and uniformly distribute them into dental matrices. The photo-curing behaviors of the Bis-GMA/TEGDMA/FS resins were monitored in situ by RT-NIR to study the photopolymerization rate and the vinyl double bond conversion. Mechanical properties (flexural strength, elastic modulus and work of fracture) of the nano FS reinforced resins/composites were tested, and Analysis of Variance (ANOVA) was used for the statistical analysis of the acquired data. The morphology of nano FS and the representative fracture surfaces of its reinforced resins/composites were examined by SEM/TEM. Results Impregnation of small mass fractions (1 % and 2.5 %) of nano FS into Bis-GMA/TEGDMA (50/50 mass ratio) dental resins/composites improved the mechanical properties substantially. Larger mass fraction of impregnation (7.5 %), however, did not further improve the mechanical properties (one way ANOVA, P > 0.05) and may even reduce the mechanical properties. The high degree of separation and uniform distribution of nano FS into dental resins/composites was a challenge. Impregnation of nano FS into dental resins/composites could result in two opposite effects: a reinforcing effect due to the highly separated and uniformly distributed nano FS single crystals, or a weakening effect due to the formation of FS agglomerates/particles. Significance Uniform distribution of highly separated nano FS single crystals into dental resins/composites could significantly improve the mechanical properties of the resins/composites. PMID:17572485

Enriched continental flood basalts from depleted mantle melts: modeling the lithospheric contamination of Karoo lavas from Antarctica

NASA Astrophysics Data System (ADS)

Heinonen, Jussi S.; Luttinen, Arto V.; Bohrson, Wendy A.

2016-01-01

Continental flood basalts (CFBs) represent large-scale melting events in the Earth's upper mantle and show considerable geochemical heterogeneity that is typically linked to substantial contribution from underlying continental lithosphere. Large-scale partial melting of the cold subcontinental lithospheric mantle and the large amounts of crustal contamination suggested by traditional binary mixing or assimilation-fractional crystallization models are difficult to reconcile with the thermal and compositional characteristics of continental lithosphere, however. The well-exposed CFBs of Vestfjella, western Dronning Maud Land, Antarctica, belong to the Jurassic Karoo large igneous province and provide a prime locality to quantify mass contributions of lithospheric and sublithospheric sources for two reasons: (1) recently discovered CFB dikes show isotopic characteristics akin to mid-ocean ridge basalts, and thus help to constrain asthenospheric parental melt compositions and (2) the well-exposed basaltic lavas have been divided into four different geochemical magma types that exhibit considerable trace element and radiogenic isotope heterogeneity (e.g., initial ɛ Nd from -16 to +2 at 180 Ma). We simulate the geochemical evolution of Vestfjella CFBs using (1) energy-constrained assimilation-fractional crystallization equations that account for heating and partial melting of crustal wall rock and (2) assimilation-fractional crystallization equations for lithospheric mantle contamination by using highly alkaline continental volcanic rocks (i.e., partial melts of mantle lithosphere) as contaminants. Calculations indicate that the different magma types can be produced by just minor (1-15 wt%) contamination of asthenospheric parental magmas by melts from variable lithospheric reservoirs. Our models imply that the role of continental lithosphere as a CFB source component or contaminant may have been overestimated in many cases. Thus, CFBs may represent major juvenile crustal growth events rather than just recycling of old lithospheric materials.

Fabrication and evaluation of Bis-GMA/TEGDMA dental resins/composites containing nano fibrillar silicate.

PubMed

Tian, Ming; Gao, Yi; Liu, Yi; Liao, Yiliang; Hedin, Nyle E; Fong, Hao

2008-02-01

To investigate the reinforcement of Bis-GMA/TEGDMA dental resins (without conventional glass filler) and composites (with conventional glass filler) with various mass fractions of nano fibrillar silicate (FS). Three dispersion methods were studied to separate the silanized FS as nano-scaled single crystals and uniformly distribute them into dental matrices. The photo-curing behaviors of the Bis-GMA/TEGDMA/FS resins were monitored in situ by RT-NIR to study the photopolymerization rate and the vinyl double bond conversion. Mechanical properties (flexural strength, elastic modulus and work-of-fracture) of the nano FS reinforced resins/composites were tested, and analysis of variance (ANOVA) was used for the statistical analysis of the acquired data. The morphology of nano FS and the representative fracture surfaces of its reinforced resins/composites were examined by SEM/TEM. Impregnation of small mass fractions (1% and 2.5%) of nano FS into Bis-GMA/TEGDMA (50/50 mass ratio) dental resins/composites improved the mechanical properties substantially. Larger mass fraction of impregnation (7.5%), however, did not further improve the mechanical properties (one way ANOVA, P>0.05) and may even reduce the mechanical properties. The high degree of separation and uniform distribution of nano FS into dental resins/composites was a challenge. Impregnation of nano FS into dental resins/composites could result in two opposite effects: a reinforcing effect due to the highly separated and uniformly distributed nano FS single crystals, or a weakening effect due to the formation of FS agglomerates/particles. Uniform distribution of highly separated nano FS single crystals into dental resins/composites could significantly improve the mechanical properties of the resins/composites.

Set-up of an XAFS beamline for measurements between 2.4-8 keV at DORIS III

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

Welter, Edmund

2010-06-23

In this paper results from the commissioning phase and from first user experiments of a new EXAFS beamline at the DORIS III storage ring are presented. The bending magnet EXAFS beamline A1 underwent a complete rebuild and now covers the energy range 2.4-8 keV. A Ni-coated toroidal mirror, placed in a 2:1 focusing position and a plane mirror with one Ni coated stripe and one uncoated (SiO{sub 2}) stripe are used for effective higher harmonics suppression and focusing. The UHV-compatible fixed-exit Double Crystal Monochromator (DCM) is equipped with two Si(111) crystal pairs. The second crystal of one of the twomore » crystal pairs is tilted by 90 deg. around the surface normal to shift the position of glitches. It allows Bragg angles between 5 deg. and 55.5 deg. and continuous scans in quick-EXAFS mode. Test measurements during the commissioning phase proved the excellent performance of the monochromator and a high quality of the XAFS spectra over the entire working range.« less

Iron isotope fractionation during magmatic differentiation in Kilauea Iki lava lake.

PubMed

Teng, Fang-Zhen; Dauphas, Nicolas; Helz, Rosalind T

2008-06-20

Magmatic differentiation helps produce the chemical and petrographic diversity of terrestrial rocks. The extent to which magmatic differentiation fractionates nonradiogenic isotopes is uncertain for some elements. We report analyses of iron isotopes in basalts from Kilauea Iki lava lake, Hawaii. The iron isotopic compositions (56Fe/54Fe) of late-stagemeltveins are 0.2 permil (per thousand) greater than values for olivine cumulates. Olivine phenocrysts are up to 1.2 per thousand lighter than those of whole rocks. These results demonstrate that iron isotopes fractionate during magmatic differentiation at both whole-rock and crystal scales. This characteristic of iron relative to the characteristics of magnesium and lithium, for which no fractionation has been found, may be related to its complex redox chemistry in magmatic systems and makes iron a potential tool for studying planetary differentiation.

Iron isotope fractionation during magmatic differentiation in Kilauea Iki lava lake

USGS Publications Warehouse

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

2008-01-01

Magmatic differentiation helps produce the chemical and petrographic diversity of terrestrial rocks. The extent to which magmatic differentiation fractionates nonradiogenic isotopes is uncertain for some elements. We report analyses of iron isotopes in basalts from Kilauea Iki lava lake, Hawaii. The iron isotopic compositions (56Fe/54Fe) of late-stage melt veins are 0.2 per mil (???) greater than values for olivine cumulates. Olivine phenocrysts are up to 1.2??? lighter than those of whole rocks. These results demonstrate that iron isotopes fractionate during magmatic differentiation at both whole-rock and crystal scales. This characteristic of iron relative to the characteristics of magnesium and lithium, for which no fractionation has been found, may be related to its complex redox chemistry in magmatic systems and makes iron a potential tool for studying planetary differentiation.

Energy minimization in nematic liquid crystal systems driven by geometric confinement and temperature gradients with applications in colloidal systems

NASA Astrophysics Data System (ADS)

Kolacz, Jakub

We first explore the topology of liquid crystals and look at the fundamental limitations of liquid crystals in confined geometries. The properties of liquid crystal droplets are studied both theoretically and through simulations. We then demonstrate a method of chemically patterning surfaces that allows us to generate periodic arrays of micron-sized liquid crystal droplets and compare them to our simulation results. The parallelizable method of self-localizing liquid crystals using 2D chemical patterning developed here has applications in liquid crystal biosensors and lens arrays. We also present the first work looking at colloidal liquid crystals under the guise of thermophoresis. We observe that strong negative thermophoresis occurs in these systems and develop a theory based on elastic energy minimization. We also calculate a Soret coefficient two orders of magnitude larger than those present in the literature. This large Soret coefficient has considerable potential for improving thermophoretic sorting mechanisms such as Thermal-Field Flow Fractionation and MicroScale Thermophoresis. The final piece of this work demonstrates a method of using projection lithography to polymerize liquid crystal colloids with a defined internal director. While still a work in progress, there is potential for generating systems of active colloids that can change shape upon external stimulus and in the generation of self-folding shapes by selective polymerization and director predetermination in the vain of micro-kirigami.

Impact of Major Pulmonary Resections on Right Ventricular Function: Early Postoperative Changes.

PubMed

Elrakhawy, Hany M; Alassal, Mohamed A; Shaalan, Ayman M; Awad, Ahmed A; Sayed, Sameh; Saffan, Mohammad M

2018-01-15

Right ventricular (RV) dysfunction after pulmonary resection in the early postoperative period is documented by reduced RV ejection fraction and increased RV end-diastolic volume index. Supraventricular arrhythmia, particularly atrial fibrillation, is common after pulmonary resection. RV assessment can be done by non-invasive methods and/or invasive approaches such as right cardiac catheterization. Incorporation of a rapid response thermistor to pulmonary artery catheter permits continuous measurements of cardiac output, right ventricular ejection fraction, and right ventricular end-diastolic volume. It can also be used for right atrial and right ventricular pacing, and for measuring right-sided pressures, including pulmonary capillary wedge pressure. This study included 178 patients who underwent major pulmonary resections, 36 who underwent pneumonectomy assigned as group (I) and 142 who underwent lobectomy assigned as group (II). The study was conducted at the cardiothoracic surgery department of Benha University hospital in Egypt; patients enrolled were operated on from February 2012 to February 2016. A rapid response thermistor pulmonary artery catheter was inserted via the right internal jugular vein. Preoperatively the following was recorded: central venous pressure, mean pulmonary artery pressure, pulmonary capillary wedge pressure, cardiac output, right ventricular ejection fraction and volumes. The same parameters were collected in fixed time intervals after 3 hours, 6 hours, 12 hours, 24 hours, and 48 hours postoperatively. For group (I): There were no statistically significant changes between the preoperative and postoperative records in the central venous pressure and mean arterial pressure; there were no statistically significant changes in the preoperative and 12, 24, and 48 hour postoperative records for cardiac index; 3 and 6 hours postoperative showed significant changes. There were statistically significant changes between the preoperative and postoperative records for heart rate, mean pulmonary artery pressure, pulmonary capillary wedge pressure, pulmonary vascular resistance, right ventricular ejection fraction and right ventricular end diastolic volume index, in all postoperative records. For group (II): There were no statistically significant changes between the preoperative and all postoperative records for the central venous pressure, mean arterial pressure and cardiac index. There were statistically significant changes between the preoperative and postoperative records for heart rate, mean pulmonary artery pressure, pulmonary capillary wedge pressure, pulmonary vascular resistance, right ventricular ejection fraction and right ventricular end diastolic volume index in all postoperative records. There were statistically significant changes between the two groups in all postoperative records for heart rate, mean pulmonary artery pressure, pulmonary capillary wedge pressure, pulmonary vascular resistance, right ventricular ejection fraction and right ventricular end diastolic volume index. There is right ventricular dysfunction early after major pulmonary resection caused by increased right ventricular afterload. This dysfunction is more present in pneumonectomy than in lobectomy. Heart rate, mean pulmonary artery pressure, pulmonary capillary wedge pressure, pulmonary vascular resistance, right ventricular ejection fraction, and right ventricular end diastolic volume index are significantly affected by pulmonary resection.

Effects-driven chemical fractionation of heavy fuel oil to isolate compounds toxic to trout embryos.

PubMed

Bornstein, Jason M; Adams, Julie; Hollebone, Bruce; King, Thomas; Hodson, Peter V; Brown, R Stephen

2014-04-01

Heavy fuel oil (HFO) spills account for approximately 60% of ship-source oil spills and are up to 50 times more toxic than medium and light crude oils. Heavy fuel oils contain elevated concentrations of polycyclic aromatic hydrocarbons (PAHs) and alkyl-PAHs, known to be toxic to fish; however, little direct characterization of HFO toxicity has been reported. An effects-driven chemical fractionation was conducted on HFO 7102 to separate compounds with similar chemical and physical properties, including toxicity, to isolate the groups of compounds most toxic to trout embryos. After each separation, toxicity tests directed the next phase of fractionation, and gas chromatography-mass spectrometry analysis correlated composition with toxicity, with a focus on PAHs. Low-temperature vacuum distillation permitted the separation of HFO into 3 fractions based on boiling point ranges. The most toxic of these fractions underwent wax precipitation to remove long-chain n-alkanes. The remaining PAH-rich extract was further separated using open column chromatography, which provided distinct fractions that were grouped according to increasing aromatic ring count. The most toxic of these fractions was richest in PAHs and alkyl-PAHs. The results of the present study were consistent with previous crude oil studies that identified PAH-rich fractions as the most toxic. © 2013 SETAC.

A Re-appraisal of Olivine Sorting and Accumulation in Hawaiian Magmas.

NASA Astrophysics Data System (ADS)

Rhodes, J. M.

2002-12-01

Bowen never used the m-words (magma mixing) in his highly influential book "The Origin of the Igneous Rocks". Yet, in the past 20-30 years, magma mixing has been proposed as an important, almost ubiquitous, process at volcanoes in all tectonic environments ranging from oceanic basalts to large silicic magma bodies, and as the possible trigger of eruptions. Bowen regarded Hawaiian olivine basalts and picrites as the result of olivine accumulation in a lower MgO magma that was crystallizing and fractionating olivine. This, with variants, has been the party line ever since, the only debate being over the MgO content of the proposed parental magmas. Although magma mixing has been recognized as an important process in differentiated, low-MgO (below 7 percent), Hawaiian magmas, the wide range in MgO (7-30 percent) in Hawaiian olivine tholeiites and picrites is invariably attributed to olivine crystallization, fractionation and accumulation. In this paper I will re-evaluate this hypothesis using well-documented examples from Kilauea, Mauna Kea and Mauna Loa that exhibit well-defined, coherent linear trends of major oxides and trace elements with MgO . If olivine control is the only factor responsible for these trends, then the intersection of the regression lines for each trend should intersect olivine compositions at a common forsterite composition, corresponding to the average accumulated olivine in each of the magmas. In some cases (the ongoing Puu Oo eruption) this simple test holds and olivine fractionation and accumulation can clearly be shown to be the dominant process. In other examples from Mauna Kea and Mauna Loa (1852, 1868, 1950 eruptions, and Mauna Loa in general) the test does not hold, and a more complicated process is required. Additionally, for those magmas that fail the test, CaO/Al2O3 invariably decreases with decreasing MgO content. This should not happen if only olivine fractionation and accumulation are involved. The explanation for these linear trends that approach, but fail to intersect, appropriate olivine compositions is a combination of magma mixing accompanied by olivine crystallization and accumulation. One of the mixing components is a is a high-MgO (about13-15 percent) magma laden with olivine phenocrysts and xenocrysts and the other is a consanguineous low-MgO (about 7 percent) quasi "steady-state" magma, with a prior history of clinopyroxene and plagioclase fractionation.

Subcellular distribution of uranium in the roots of Spirodela punctata and surface interactions

NASA Astrophysics Data System (ADS)

Nie, Xiaoqin; Dong, Faqin; Liu, Ning; Liu, Mingxue; Zhang, Dong; Kang, Wu; Sun, Shiyong; Zhang, Wei; Yang, Jie

2015-08-01

The subcellular distribution of uranium in roots of Spirodela punctata (duckweed) and the process of surface interaction were studied upon exposure to U (0, 5-200 mg/L) at pH 5. The concentration of uranium in each subcelluar fraction increased significantly with increasing solution U level, after 200 mg/L uranium solution treatment 120 h, the proportion of uranium concentration approximate as 8:2:1 in the cell wall organelle and cytosol fractions of roots of S. punctata. OM SEM and EDS showed after 5-200 mg/L U treatment 4-24 h, some intracellular fluid released from the root cells, after 100 mg/L U treatment 48 h, the particles including 35% Fe (wt%) and other organic matters such as EPS released from the cells, most of the uranium bound onto the root surface and contacted with phosphorus ligands and formed as nano-scales U-P lamellar crystal, similar crystal has been found in the cell wall and organelle fractions after 50 mg/L U treatment 120 h. FTIR and XPS analyses result indicates the uranium changed the band position and shapes of phosphate group, and the region of characteristic peak belongs to U(VI) and U(IV) were also observed.

A comparative study of the influence of alpha-lactose monohydrate particle morphology on granule and tablet properties after roll compaction/dry granulation.

PubMed

Grote, Simon; Kleinebudde, Peter

2018-05-29

The influence of particle morphology and size of alpha-lactose monohydrate on dry granules and tablets was studied. Four different morphologies were investigated: Two grades of primary crystals, which differed in their particle size and structure (compact crystals vs. agglomerates). The materials were roll compacted at different specific compaction forces and changes in the particle size distribution and the specific surface area were measured. Afterwards, two fractions of granules were pressed to tablets and the tensile strength was compared to that from tablets compressed from the raw materials. The specific surface area was increased induced by roll compaction/dry granulation for all materials. At increased specific compaction forces, the materials showed sufficient size enlargement. The morphology of lactose determined the strength of direct compressed tablets. In contrast, the strength of granule tablets was leveled by the previous compression step during roll compaction/dry granulation. Thus, the tensile strength of tablets compressed directly from the powder mixtures determined whether materials exhibited a loss in tabletability after roll compaction/dry granulation or not. The granule size had only a slight influence on the strength of produced tablets. In some cases, the fraction of smaller granules showed a higher tensile strength compared to the larger fraction.

Zinc isotope fractionation during magmatic differentiation and the isotopic composition of the bulk Earth

USGS Publications Warehouse

Chen, Heng; Savage, Paul S.; Teng, Fang-Zehn; Helz, Rosalind T.; Moynier, Frédéric

2013-01-01

he zinc stable isotope system has been successfully applied to many and varied fields in geochemistry, but to date it is still not completely clear how this isotope system is affected by igneous processes. In order to evaluate the potential application of Zn isotopes as a proxy for planetary differentiation and volatile history, it is important to constrain the magnitude of Zn isotopic fractionation induced by magmatic differentiation. In this study we present high-precision Zn isotope analyses of two sets of chemically diverse, cogenetic samples from Kilauea Iki lava lake, Hawaii, and Hekla volcano, Iceland, which both show clear evidence of having undergone variable and significant degrees of magmatic differentiation. The Kilauea Iki samples display small but resolvable variations in Zn isotope composition (0.26‰66Zn66Zn defined as the per mille deviation of a sample's 66Zn/64Zn compositional ratio from the JMC-Lyon standard), with the most differentiated lithologies exhibiting more positive δ66Zn values. This fractionation is likely a result of the crystallization of olivine and/or Fe–Ti oxides, which can both host Zn in their crystal structures. Samples from Hekla have a similar range of isotopic variation (0.22‰66Zn66Zn=0.28±0.05‰ (2s.d.).

Group IVA irons: New constraints on the crystallization and cooling history of an asteroidal core with a complex history

NASA Astrophysics Data System (ADS)

McCoy, T. J.; Walker, R. J.; Goldstein, J. I.; Yang, J.; McDonough, W. F.; Rumble, D.; Chabot, N. L.; Ash, R. D.; Corrigan, C. M.; Michael, J. R.; Kotula, P. G.

2011-11-01

We report analyses of 14 group IVA iron meteorites, and the ungrouped but possibly related, Elephant Moraine (EET) 83230, for siderophile elements by laser ablation ICP-MS and isotope dilution. EET was also analyzed for oxygen isotopic composition and metallographic structure, and Fuzzy Creek, currently the IVA with the highest Ni concentration, was analyzed for metallographic structure. Highly siderophile elements (HSE) Re, Os and Ir concentrations vary by nearly three orders of magnitude over the entire range of IVA irons, while Ru, Pt and Pd vary by less than factors of five. Chondrite normalized abundances of HSE form nested patterns consistent with progressive crystal-liquid fractionation. Attempts to collectively model the HSE abundances resulting from fractional crystallization achieved best results for 3 wt.% S, compared to 0.5 or 9 wt.% S. Consistent with prior studies, concentrations of HSE and other refractory siderophile elements estimated for the bulk IVA core and its parent body are in generally chondritic proportions. Projected abundances of Pd and Au, relative to more refractory HSE, are slightly elevated and modestly differ from L/LL chondrites, which some have linked with group IVA, based on oxygen isotope similarities. Abundance trends for the moderately volatile and siderophile element Ga cannot be adequately modeled for any S concentration, the cause of which remains enigmatic. Further, concentrations of some moderately volatile and siderophile elements indicate marked, progressive depletions in the IVA system. However, if the IVA core began crystallization with ˜3 wt.% S, depletions of more volatile elements cannot be explained as a result of prior volatilization/condensation processes. The initial IVA core had an approximately chondritic Ni/Co ratio, but a fractionated Fe/Ni ratio of ˜10, indicates an Fe-depleted core. This composition is most easily accounted for by assuming that the surrounding silicate shell was enriched in iron, consistent with an oxidized parent body. The depletions in Ga may reflect decreased siderophilic behavior in a relatively oxidized body, and more favorable partitioning into the silicate portion of the parent body. Phosphate inclusions in EET show Δ 17O values within the range measured for silicates in IVA iron meteorites. EET has a typical ataxitic microstructure with precipitates of kamacite within a matrix of plessite. Chemical and isotopic evidence for a genetic relation between EET and group IVA is strong, but the high Ni content and the newly determined, rapid cooling rate of this meteorite show that it should continue to be classified as ungrouped. Previously reported metallographic cooling rates for IVA iron meteorites have been interpreted to indicate an inwardly crystallizing, ˜150 km radius metallic body with little or no silicate mantle. Hence, the IVA group was likely formed as a mass of molten metal separated from a much larger parent body that was broken apart by a large impact. Given the apparent genetic relation with IVA, EET was most likely generated via crystal-liquid fractionation in another, smaller body spawned from the same initial liquid during the impact event that generated the IVA body.

Les premières phases d'édification du stratovolcan du Cantal (Massif central, France) entre 9,5 et 8,0Ma : géologie et géochimie du secteur de l'ÉlancèzeFirst stage of the Cantal stratovolcano (Massif Central, France) construction between 9.5 and 8.0Ma: geology and geochemistry of the Élancèze area

NASA Astrophysics Data System (ADS)

Legendre, Christelle; Caroff, Martial; Leyrit, Hervé; Nehlig, Pierre; Thièblemont, Denis

2001-05-01

Recent cartography of the Élancèze area resulted in the identification of a residual ancient topographic relief comprised of basaltic and intermediate silica-saturated lavas partly covered by brecciated formations, emplaced during the first stage of edification of the Cantal stratovolcano (9.5-8.0 Ma). The ancient relief has been the subject of a specified petrological study. Although the corresponding mineralogical and geochemical data are rather consistent with the assumption of a differentiation mainly governed by fractional crystallization, the study of some incompatible trace element diagrams suggests that this process cannot have occurred in closed-system. A model of crustal assimilation coupled with fractional crystallization involving an amphibole-bearing cumulate is proposed.

Modelling Equilibrium and Fractional Crystallization in the System MgO-FeO-CaO-Al2O3-SiO2

NASA Technical Reports Server (NTRS)

Herbert, F.

1985-01-01

A mathematical modelling technique for use in petrogenesis calculations in the system MgO-FeO-CaO-Al2O3-SiO2 is reported. Semiempirical phase boundary and elemental distribution information was combined with mass balance to compute approximate equilibrium crystallization paths for arbitrary system compositions. The calculation is applicable to a range of system compositions and fractionation calculations are possible. The goal of the calculation is the computation of the composition and quantity of each phase present as a function of the degree of solidification. The degree of solidification is parameterized by the heat released by the solidifying phases. The mathematical requirement for the solution of this problem is: (1) An equation constraining the composition of the magma for each solid phase in equilibrium with the liquidus phase, and (2) an equation for each solid phase and each component giving the distribution of that element between that phase and the magma.

High alumina (HA) and very high potassium (VHK) basalt clasts from Apollo 14 breccias. II - Whole rock geochemistry - Further evidence for combined assimilation and fractional crystallization within the lunar crust

NASA Technical Reports Server (NTRS)

Neal, C. R.; Taylor, L. A.; Schmitt, R. A.; Hughes, S. S.; Lindstrom, M. M.

1989-01-01

The understanding of basalt petrogenesis at the Apollo 14 site has increased markedly due to the study of 'new' samples from breccia 'pull-apart' efforts. Whole-rock compositions of 26 new high alumina (HA) and 7 very high potassium (VHK) basalts emphasize the importance of combined assimilation and fractional crystallization in a lunar regime. Previously formulated models for HA and VHK basalt petrogenesis are modified in order to accomodate these new data, although modeling parameters are essentially the same. The required range in HA basalt compositions is generated by the assimilation of KREEP by a 'primitive' parental magma. The VHK basalts can be generated by three parental HA basalts assimilating granite. Results indicate that VHK basalt compositions are dominated by the parental magma, and only up to 8 percent granite assimilation is required. This modeling indicates that at least three VHK basalt flows must be present at the Apollo 14 site.

Insights into the Role of Heme in the Mechanism of Action of Antimalarials

PubMed Central

Combrinck, Jill M.; Mabotha, Tebogo E.; Ncokazi, Kanyile K.; Ambele, Melvin A.; Taylor, Dale; Smith, Peter J.; Hoppe, Heinrich C.; Egan, Timothy J.

2012-01-01

Using cell fractionation and measurement of Fe(III)heme-pyridine, the antimalarial chloroquine (CQ) has been shown to cause a dose-dependent decrease in hemozoin and concomitant increase in toxic “free” heme in cultured Plasmodium falciparum that is directly correlated with parasite survival. Transmission electron microscopy techniques have further shown that heme is redistributed from the parasite digestive vacuole to the cytoplasm and that CQ disrupts hemozoin crystal growth, resulting in mosaic boundaries in the crystals formed in the parasite. Extension of the cell fractionation study to other drugs has shown that artesunate, amodiaquine, lumefantrine, mefloquine and quinine, all clinically important antimalarials, also inhibit hemozoin formation in the parasite cell, while the antifolate pyrimethamine and its combination with sulfadoxine do not. This study finally provides direct evidence in support of the hemozoin inhibition hypothesis for the mechanism of action of CQ and shows that other quinoline and related antimalarials inhibit cellular hemozoin formation. PMID:23043646

Petrology of gabbroic rocks from the Mid-Cayman rise spreading center

NASA Technical Reports Server (NTRS)

Elthon, Don

1987-01-01

Mineral analyses of oxide and silicate phases from a suite (collected with the DSRV Alvin in January 1976 and July 1977) of 48 gabbroic rocks collected from the vicinity of the Mid-Cayman Rise spreading center are reported. Mineral compositions of these anorthosites, leuco-troctolite, leuco-olivine gabbros, olivine gabbros, leuco-gabbros, and gabbros indicate the cumulate rocks have been produced by the crystal fractionation of basaltic liquids. Certain features of these rocks are inconsistent with the occurrence of this fractionation at low pressures (1 atm to 2 kbar). Although the experimental data are not available to conclusively demonstrate that the effects seen were produced at moderate pressures (5-10 kbar), the effects are similar to those predicted thermodynamically and to those observed in limited experimental studies within this pressure range. It is therefore suggested that the most likely scenario for the production of these gabbroic rocks is the moderate-pressure crystallization of basaltic magmas within deep-seated magma chambers underneath this slow-spreading center.

Photonic Crystal Based Sensor for Organic Solvents and for Solvent-Water Mixtures

PubMed Central

Fenzl, Christoph; Hirsch, Thomas; Wolfbeis, Otto S.

2012-01-01

Monodisperse polystyrene nanoparticles with a diameter of 173 nm were incorporated into a polydimethylsiloxane matrix where they display an iridescent color that can be attributed to the photonic crystal effect. The film is of violet color if placed in plain water, but turns to red in the presence of the non-polar solvent n-hexane. Several solvents were studied in some detail. We show that such films are capable of monitoring the water content of ethanol/water mixtures, where only 1% (v/v) of water leads to a shift of the peak wavelength of reflected light by 5 nm. The method also can be applied to determine, both visually and instrumentally, the fraction of methanol in ethanol/methanol mixtures. Here, a fraction of 1% of methanol (v/v) results in a wavelength shift of 2 nm. The reflected wavelength is not influenced by temperature changes nor impeded by photobleaching. The signal changes are fully reversible and response times are <1 s. PMID:23235441

Dispersion Stability of O/W Emulsions with Different Oil Contents Under Various Freezing and Thawing Conditions.

PubMed

Katsuki, Kazutaka; Miyagawa, Yayoi; Nakagawa, Kyuya; Adachi, Shuji

2017-07-01

Freezing and thawing of oil-in-water (O/W) emulsion-type foods bring about oil-water separation and deterioration; hence, the effects of freezing and thawing conditions on the destabilization of O/W emulsions were examined. The freezing rate and thawing temperature hardly affected the stability of the O/W emulsion. O/W emulsions having different oil fractions were stored at temperatures ranging from -30 to -20 °C and then thawed. The stability after thawing depended on the storage temperature, irrespective of the oil fraction of the emulsion. A good correlation was found between the time at which the stability began to decrease and the time taken for the oil to crystalize. These results indicated that the dominant cause for the destabilization of the O/W emulsion during freezing and thawing is the crystallization of the oil phase and that the effects of the freezing and thawing rates on the stability are insignificant. © 2017 Institute of Food Technologists®.

Petrogenesis of mare basalts - A record of lunar volcanism

NASA Astrophysics Data System (ADS)

Neal, Clive R.; Taylor, Lawrence A.

1992-06-01

The classification, sources, and overall petrogenesis of mare basalts are reviewed. All mare basalt analyses are used to define a sixfold classification scheme using TiO2 contents as the primary division. A secondary division is made using Al2O3 contents, and a tertiary division is defined using K contents. Such divisions and subdivisions yield a classification containing 12 categories, of which six are accounted for by the existing Apollo and Luna collections. A variety of postmagma-generation such as fractional crystallization, either alone or combined with wallrock assimilation, are invoked to explain the compositional ranges of the various mare basalt suites. High-Ti mare basalts are found at Apollo 1 and Apollo 17 sites; the A-11 basalts contain lower TiO2 abundances, a considerably larger range in trace-element contents, and the only occurrence of high-Ti/high-K mare basalts. The low-Ti basalts exhibit a wide range of major-and trace-element compositions and require source heterogeneity, fractional crystallization, and some assimilation.

Effect of microstructure on the coupled electromagnetic-thermo-mechanical response of cyclotrimethylenetrinitramine-estane energetic aggregates to infrared laser radiation

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

Brown, Judith A.; Zikry, M. A., E-mail: zikry@ncsu.edu

2015-09-28

The coupled electromagnetic (EM)-thermo-mechanical response of cyclotrimethylenetrinitramine-estane energetic aggregates under laser irradiation and high strain rate loads has been investigated for various aggregate sizes and binder volume fractions. The cyclotrimethylenetrinitramine (RDX) crystals are modeled with a dislocation density-based crystalline plasticity formulation and the estane binder is modeled with finite viscoelasticity through a nonlinear finite element approach that couples EM wave propagation with laser heat absorption, thermal conduction, and inelastic deformation. Material property and local behavior mismatch at the crystal-binder interfaces resulted in geometric scattering of the EM wave, electric field and laser heating localization, high stress gradients, dislocation density, andmore » crystalline shear slip accumulation. Viscous sliding in the binder was another energy dissipation mechanism that reduced stresses in aggregates with thicker binder ligaments and larger binder volume fractions. This investigation indicates the complex interactions between EM waves and mechanical behavior, for accurate predictions of laser irradiation of heterogeneous materials.« less

[Waist-hip ratio and perioperative bleeding in patients who underwent radical prostatectomy].

PubMed

León-Ramírez, Víctor; Santiago-López, Janaí; Reyes-Rivera, Juan Gabriel; Miguel-Soto, Edgar

2016-01-01

Radical prostatectomy is associated with perioperative bleeding and multiple transfusions. Abdominal obesity is a perioperative risk factor. We suggest that the adipocytes have a protective effect in oncological patients undergoing radical prostatectomy. The aim was to evaluate the effect of waist-hip ratio (WHR) on the amount of bleeding and perioperative transfusion requirements in oncological patients undergoing radical prostatectomy. We performed a cohort study in 156 patients. We had two groups: the control group (WHR<0.95) and the problem group (WHR≥0.95). Blood loss and fractions transfused during surgery and in the postoperative period were recorded. In the analysis of variables, for descriptive statistics we used measures of central tendency and dispersion. Inferential statistics was obtained by chi square, Student's t test, Mann-Whitney U and ANOVA. A p<0.05 was significant. We found significant differences in weight, body mass index, waist, WHR, perioperative bleeding, fractions transfused, permanence of the catheter, and hospital days. Patients who underwent radical prostatectomy with a WHR≥0.95 had a magnitude of perioperative bleeding and transfusion requirements with a WHR<0.95.

Chemoembolic Hepatopulmonary Shunt Reduction to Allow Safe Yttrium-90 Radioembolization Lobectomy of Hepatocellular Carcinoma

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

Gaba, Ron C., E-mail: rgaba@uic.edu; VanMiddlesworth, Kyle A.

2012-12-15

Yttrium-90 ({sup 90}Y) radioembolization represents an emerging transcatheter treatment option for the management of hepatocellular carcinoma (HCC). Elevation of the hepatopulmonary shunt fraction risks nontarget radiation to the lungs and may limit the use of {sup 90}Y therapy in patients with locally advanced disease with vascular invasion, who often demonstrate increased shunting. We present two cases in which patients with HCC and portal vein invasion resulting in elevated hepatopulmonary shunt fractions underwent chemoembolic shunt closure to allow safe {sup 90}Y radioembolization. Both patients demonstrated excellent tumor response and patient survival. On this basis, we propose a role for chemoembolic reductionmore » of the lung shunt fraction before {sup 90}Y radioembolization in patients with extensive tumor-related hepatopulmonary shunting.« less

Transient rheology of crystallizing andesitic magmas

NASA Astrophysics Data System (ADS)

de Biasi, L. J.; Chevrel, M. O.; Hanson, J. B.; Cimarelli, C.; Lavallée, Y.; Dingwell, D. B.

2012-04-01

The viscosity of magma strongly influences its rheological behaviour, which is a key determinant of magma transport processes and volcanic eruptions. Understanding the factors controlling the viscosity of magma is important to our assessment of hazards posed by active volcanoes. In nature, magmas span a very wide range in viscosity (10-1 to 1014 Pa s), depending on chemical composition (including volatile content), temperature, and importantly, crystal fraction, which further induces a complex strain rate dependence (i.e. non-Newtonian rheology). Here, we present results of transient viscosities of a crystallizing andesitic melt (57 wt.% SiO2) from Tungurahua volcano (Ecuador). We followed the experimental method developed by Vona et al. (2011) for the concentric cylinder apparatus, but optimized its implementation by leaving the spindle in situ before quenching the experimental products, to preserve the complete developed texture of the sample. The viscosity is investigated under super-liquidus (1400 ° C) and sub-liquidus temperatures (1162 and 1167 ° C). For each temperature increment, thermal equilibrium is achieved over a period of days while the spindle constantly stirs the magma. Simultaneous monitoring of the torque is used to calculate the apparent viscosity of the transient suspension. To get a better understanding of the nucleation and crystal growth processes that are involved at sub-liquidus conditions, further time-step experiments were carried out, where the samples were quenched at various equilibration stages. The mineralogical assemblage, as well as the crystal fraction, distribution and preferential alignment were then quantitatively analyzed. At temperatures below the liquidus, the suspension shows a progressive, but irregular increase of the relative shear viscosity. First, the viscosity slightly increases, possibly due to the crystallization of small, equant oxides and the formation of plagioclase nuclei. After some time (1.5-2.5 days), crystallization of large, tabular plagioclase begins, inducing a significantly stronger increase in apparent viscosity until thermo-chemical equilibration is achieved. After continued stirring the apparent viscosity slightly decreases, likely due to increasing crystal alignment. The analysis of pre-equilibrium quenched samples indicates that crystals nucleate and grow preferentially in proximity to both the spindle and the crucible wall. Furthermore, decreasing the stirring rate (aka strain rate) results in an increase in the apparent viscosity, which evidences the non-Newtonian characteristics of the magmatic suspension. In conclusion, these experiments indicate that natural andesitic magmas undergo significant rheological changes at the onset of crystallization. The observed thermo-chemical variations elucidate a transient viscosity, which deserves consideration into all problems of magma transport. Reference: Vona, A., Romano, C., Dingwell, D.B., Giordano, D. 2011. The rheology of crystal-bearing basaltic magmas from Stromboli and Etna. Geochim. Cosmochim. Acta, 75, 3214-3236.

Tracing the HIMU component within Pan-African lithosphere beneath northeast Africa: Evidence from Late Cretaceous Natash alkaline volcanics, Egypt

NASA Astrophysics Data System (ADS)

Abu El-Rus, M. A.; Chazot, G.; Vannucci, R.; Paquette, J.-L.

2018-02-01

A large late Cretaceous ( 90 Ma) volcanic field (the Natash volcanic province) crops out in southeast Egypt at the northwestern boundary of the Arabian-Nubian shield. The lavas are mainly of alkaline affinity and exhibit a continuous compositional range from alkali olivine basalt (AOB) to trachyte and rhyolite. All basaltic lavas in the province record various extents of fractional crystallization of olivine, clinopyroxene, plagioclase and spinel. The basaltic lavas show variations in Sr-Nd-Pb-Hf isotopic ratios [(87Sr/86Sr)i = 0.7030-0.70286; (143Nd/144Nd)i = 0.512653-0.512761; (206Pb/204Pb)i = 19.28-19.94; (177Hf-176Hf)i = 0.28274-0.28285], that correlate markedly with the major and trace element ratios and abundances. Assimilation of crustal material cannot explain these correlations, and we invoke instead melting of a multicomponent mantle source. We infer the existence of High-μ (HIMU), Enriched mantle type-I (EM-I) and Depleted mantle (DM) domains in the melting source, with a predominant contribution from the HIMU-type. We suggests further that the basaltic lavas originate from low degrees of partial melting (F < 5%) at moderate potential temperatures (TP) 1391-1425 °C and pressures of 2.0-2.6 GPa. The melting pressure estimations imply that melting entirely occurred within lithospheric mantle, most likely in the presence of residual amphibole as presence negative K-anomalies in the primitive mantle-normalized patterns of the fractionation-corrected melts. The presence of amphibole within the lithosphere is a strong evidence that the lithospheric mantle underwent metasomatic enrichment prior to melting in Late Cretaceous. This metasomatic event affected on the Pb isotopic compositions of the Natash volcanics by adding Th and U to the melting source. Time-integrated calculations to remove the decoupling between 206Pb and 207Pb isotopes that most probably resulted from the metasomatic event indicate a tentative link between the metasomatism occurring in the Pan-African lithospheric mantle and the formation of juvenile crust during the Pan-African Orogeny. A two stage evolution model is therefore proposed for volcanism in the Natash area: fluxing of the lithosphere by hydrous fluids during Pan-African Orogeny forming a hybrid lithospheric mantle that in Late Cretaceous underwent thermal erosion and melting in response to upwelling asthenosphere, possibly at the onset of the extensional fracturing preceded the doming of the Afro-Arabian Shield.

Geologic History of Asteroid 4 Vesta

NASA Technical Reports Server (NTRS)

Mittlefehldt, David W.

2014-01-01

Some types of meteorites - most irons, stony irons, some achondrites - hail from asteroids that were heated to the point where magmatism occurred within a very few million years of the formation of the earliest solids in the solar system. The largest clan of achondrites, the howardite, eucrite and diogenite (HED) meteorites, represent the crust of their parent asteroid]. Diogenites are cumulate harzburgites and orthopyroxenites from the lower crust whilst eucrites are basalts, diabases and cumulate gabbros from the upper crust. Howardites are impact-engendered breccias mostly of diogenites and eucrites. There remains only one large asteroid with a basaltic crust, 4 Vesta, which is thought to be the source of the HED clan. Differentiation models for Vesta are based on HED compositions. Proto-Vesta consisted of chondritic materials containing Al-26, a potent, short-lived heat source. Inferences from compositional data are that Vesta was melted to high degree (=50%) allowing homogenization of the silicate phase and separation of a metallic core. Convection of the silicate magma ocean allowed equilibrium crystallization, forming a harzburgitic mantle. After convective lockup occurred, melt collected between the mantle and the cool thermal boundary layer and underwent fractional crystallization forming an orthopyroxene-rich (diogenite) lower crust. The initial thermal boundary layer of chondritic material was replaced by a mafic upper crust through impact disruption and foundering. The mafic crust thickened over time as additional residual magma intrudes and penetrates the mafic crust forming plutons, dikes, sills and flows of cumulate and basaltic eucrite composition. This magmatic history may have taken only 2-3 Myr. This magma ocean scenario is at odds with a model of heat and magma transport that indicates that small degrees of melt would be rapidly expelled from source regions, precluding development of a magma ocean. Constraints from radiogenic Mg-26 distibutions suggest that the parent asteroid of HEDs was much smaller than Vesta. Thus, first-order questions regarding asteroid differentiation remain.

Crystallization modifiers in lipid systems.

PubMed

Ribeiro, Ana Paula Badan; Masuchi, Monise Helen; Miyasaki, Eriksen Koji; Domingues, Maria Aliciane Fontenele; Stroppa, Valter Luís Zuliani; de Oliveira, Glazieli Marangoni; Kieckbusch, Theo Guenter

2015-07-01

Crystallization of fats is a determinant physical event affecting the structure and properties of fat-based products. The stability of these processed foods is regulated by changes in the physical state of fats and alterations in their crystallization behavior. Problems like polymorphic transitions, oil migration, fat bloom development, slow crystallization and formation of crystalline aggregates stand out. The change of the crystallization behavior of lipid systems has been a strategic issue for the processing of foods, aiming at taylor made products, reducing costs, improving quality, and increasing the applicability and stability of different industrial fats. In this connection, advances in understanding the complex mechanisms that govern fat crystallization led to the development of strategies in order to modulate the conventional processes of fat structuration, based on the use of crystallization modifiers. Different components have been evaluated, such as specific triacyglycerols, partial glycerides (monoacylglycerols and diacylglycerols), free fatty acids, phospholipids and emulsifiers. The knowledge and expertise on the influence of these specific additives or minor lipids on the crystallization behavior of fat systems represents a focus of current interest for the industrial processing of oils and fats. This article presents a comprehensive review on the use of crystallization modifiers in lipid systems, especially for palm oil, cocoa butter and general purpose fats, highlighting: i) the removal, addition or fractionation of minor lipids in fat bases; ii) the use of nucleating agents to modify the crystallization process; iii) control of crystallization in lipid bases by using emulsifiers. The addition of these components into lipid systems is discussed in relation to the phenomena of nucleation, crystal growth, morphology, thermal behavior and polymorphism, with the intention of providing the reader with a complete panorama of the associated mechanisms with crystallization of fats and oils.

Morphology and kinetics of crystals growth in amorphous films of Cr2O3, deposited by laser ablation

NASA Astrophysics Data System (ADS)

Bagmut, Aleksandr

2018-06-01

An electron microscopic investigation was performed on the structure and kinetics of the crystallization of amorphous Cr2O3 films, deposited by pulsed laser sputtering of chromium target in an oxygen atmosphere. The crystallization was initiated by the action of an electron beam on an amorphous film in the column of a transmission electron microscope. The kinetic curves were plotted on the basis of a frame-by-frame analysis of the video recorded during the crystallization of the film. It was found that the amorphous phase - crystal phase transition in Cr2O3 films occurs as a layer polymorphic crystallization and is characterized by the values of the dimensionless relative length unit δ0 ≈ 2000-3100. The action of the electron beam initiates the formation of crystals of two basic morphological forms: disk-shaped and sickle-shaped. Growth of a disk-shaped crystals is characterized by a constant rate v and the quadratic dependence of the fraction of the crystalline phase x on the time t. Sickle-shaped crystal at an initial stage, as it grows, becomes as ring-shaped and disk-shaped crystal. The growth of a sickle-shaped crystal is characterized by normal and tangential velocity components, which depend on the time as ∼√t and as ∼1/√t respectively The end point of the arc at the interface between the amorphous and crystalline phases as the crystal grows describes a curve, which is similar to the Fermat helix. For sickle-shaped, as well as for disk-shaped crystals, the degree of crystallinity x ∼ t2.

Effects of Berberine Against Radiation-Induced Intestinal Injury in Mice

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

Li Guanghui; Zhang Yaping; Tang Jinliang

2010-08-01

Purpose: Radiation-induced intestinal injury is a significant clinical problem in patients undergoing abdominal radiotherapy (RT). Berberine has been used as an antimicrobial, anti-inflammatory, and antimotility agent. The present study investigated the protective effect of berberine against radiation-induced intestinal injury. Methods and Materials: The mice were administrated berberine or distilled water. A total of 144 mice underwent 0, 3, 6, 12, or 16 Gy single session whole-abdominal RT and 16 mice underwent 3 Gy/fraction/d for four fractions of fractionated abdominal RT. Tumor necrosis factor-{alpha}, interleukin-10, diamine oxidase, intestinal fatty acid-binding protein, malonaldehyde, and apoptosis were assayed in the mice after RT.more » The body weight and food intake of the mice receiving fractionated RT were recorded. Another 72 mice who had undergone 12, 16, or 20 Gy abdominal RT were monitored for mortality every 12 h. Results: The body weight and food intake of the mice administered with distilled water decreased significantly compared with before RT. After the same dose of abdominal RT, tumor necrosis factor-{alpha}, diamine oxidase, intestinal fatty acid-binding protein in plasma and malonalhehyde and apoptosis of the intestine were significantly greater in the control group than in the mice administered berberine (p < .05-.01). In contrast, interleukin-10 in the mice with berberine treatment was significantly greater than in the control group (p < .01). A similar result was found in the fractionated RT experiment and at different points after 16 Gy abdominal RT (p < .05-.01). Berberine treatment significantly delayed the point of death after 20 Gy, but not 16 Gy, abdominal RT (p < .01). Conclusion: Treatment with berberine can delay mortality and attenuated intestinal injury in mice undergoing whole abdominal RT. These findings could provide a useful therapeutic strategy for radiation-induced intestinal injury.« less

Influence of Fractionation Scheme and Tumor Location on Toxicities After Stereotactic Body Radiation Therapy for Large (≥5 cm) Non-Small Cell Lung Cancer: A Multi-institutional Analysis

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

Verma, Vivek; Shostrom, Valerie K.; Zhen, Weining

Purpose: To describe the impact of fractionation scheme and tumor location on toxicities in stereotactic body radiation therapy (SBRT) for ≥5-cm non-small cell lung cancer (NSCLC), as part of a multi-institutional analysis. Methods: Patients with primary ≥5-cm N0 M0 NSCLC who underwent ≤5-fraction SBRT were examined across multiple high-volume SBRT centers. Collected data included clinical/treatment parameters; toxicities were prospectively assessed at each institution according to the Common Terminology Criteria for Adverse Events. Patients treated daily were compared with those treated every other day (QOD)/other nondaily regimens. Stratification between central and peripheral tumors was also performed. Results: Ninety-two patients from 12 institutionsmore » were evaluated (2004-2016), with median follow-up of 12 months. In total there were 23 (25%) and 6 (7%) grade ≥2 and grade ≥3 toxicities, respectively. Grades 2 and 3 pulmonary toxicities occurred in 9% and 4%, respectively; 1 patient treated daily experienced grade 5 radiation pneumonitis. Of the entire cohort, 46 patients underwent daily SBRT, and 46 received QOD (n=40)/other nondaily (n=6) regimens. Clinical/treatment parameters were similar between groups; the QOD/other group was more likely to receive 3-/4-fraction schemas. Patients treated QOD/other experienced significantly fewer grade ≥2 toxicities as compared with daily treatment (7% vs 43%, P<.001). Patients treated daily also had higher rates of grade ≥2 pulmonary toxicities (P=.014). Patients with peripheral tumors (n=66) were more likely to receive 3-/4-fraction regimens than those with central tumors (n=26). No significant differences in grade ≥2 toxicities were identified according to tumor location (P>.05). Conclusions: From this multi-institutional study, toxicity of SBRT for ≥5-cm lesions is acceptable, and daily treatment was associated with a higher rate of toxicities.« less

Influence of Fractionation Scheme and Tumor Location on Toxicities After Stereotactic Body Radiation Therapy for Large (≥5 cm) Non-Small Cell Lung Cancer: A Multi-institutional Analysis.

PubMed

Verma, Vivek; Shostrom, Valerie K; Zhen, Weining; Zhang, Mutian; Braunstein, Steve E; Holland, John; Hallemeier, Christopher L; Harkenrider, Matthew M; Iskhanian, Adrian; Jabbour, Salma K; Attia, Albert; Lee, Percy; Wang, Kyle; Decker, Roy H; McGarry, Ronald C; Simone, Charles B

2017-03-15

To describe the impact of fractionation scheme and tumor location on toxicities in stereotactic body radiation therapy (SBRT) for ≥5-cm non-small cell lung cancer (NSCLC), as part of a multi-institutional analysis. Patients with primary ≥5-cm N0 M0 NSCLC who underwent ≤5-fraction SBRT were examined across multiple high-volume SBRT centers. Collected data included clinical/treatment parameters; toxicities were prospectively assessed at each institution according to the Common Terminology Criteria for Adverse Events. Patients treated daily were compared with those treated every other day (QOD)/other nondaily regimens. Stratification between central and peripheral tumors was also performed. Ninety-two patients from 12 institutions were evaluated (2004-2016), with median follow-up of 12 months. In total there were 23 (25%) and 6 (7%) grade ≥2 and grade ≥3 toxicities, respectively. Grades 2 and 3 pulmonary toxicities occurred in 9% and 4%, respectively; 1 patient treated daily experienced grade 5 radiation pneumonitis. Of the entire cohort, 46 patients underwent daily SBRT, and 46 received QOD (n=40)/other nondaily (n=6) regimens. Clinical/treatment parameters were similar between groups; the QOD/other group was more likely to receive 3-/4-fraction schemas. Patients treated QOD/other experienced significantly fewer grade ≥2 toxicities as compared with daily treatment (7% vs 43%, P<.001). Patients treated daily also had higher rates of grade ≥2 pulmonary toxicities (P=.014). Patients with peripheral tumors (n=66) were more likely to receive 3-/4-fraction regimens than those with central tumors (n=26). No significant differences in grade ≥2 toxicities were identified according to tumor location (P>.05). From this multi-institutional study, toxicity of SBRT for ≥5-cm lesions is acceptable, and daily treatment was associated with a higher rate of toxicities. Copyright © 2016 Elsevier Inc. All rights reserved.

Predicting the Sources and Formation Mechanisms of Evolved Lunar Crust by Linking K/Ca Ratios of Lunar Granites to Analogous Terrestrial Igneous Rocks

NASA Technical Reports Server (NTRS)

Mills, R. D.; Simon, J. I.

2012-01-01

Although silicic rocks (i.e. granites and rhyolites) comprise a minor component of the sampled portion of the lunar crust, recent remote sensing studies [e.g., 1-4] indicate that several un-sampled regions of the Moon have significantly higher concentrations of silicic material (also high in [K], [U], and [Th]) than sampled regions. Within these areas are morphological features that are best explained by the existence of chemically evolved volcanic rocks. Observations of silicic domes [e.g., 1-5] suggest that sizable networks of silicic melt were present during crust formation. Isotopic data indicate that silicic melts were generated over a prolonged timespan from 4.3 to 3.9 Ga [e.g., 6-8]. The protracted age range and broad distribution of silicic rocks on the Moon indicate that their petrogenesis was an important mechanism for secondary crust formation. Understanding the origin and evolution of such silicic magmas is critical to determining the composition of the lunar crustal highlands and will help to distinguish between opposing ideas for the Moon's bulk composition and differentiation. The two main hypotheses for generating silicic melts on Earth are fractional crystallization or partial melting. On the Moon silicic melts are thought to have been generated during extreme fractional crystallization involving end-stage silicate liquid immiscibility (SLI) [e.g. 9, 10]. However, SLI cannot account for the production of significant volumes of silicic melt and its wide distribution, as reported by the remote global surveys [1, 2, 3]. In addition, experimental and natural products of SLI show that U and Th, which are abundant in the lunar granites and seen in the remote sensing data of the domes, are preferentially partitioned into the depolymerized ferrobasaltic magma and not the silicic portion [11, 12]. If SLI is not the mechanism that generated silicic magmas on the Moon then alternative processes such as fractional crystallization (only crystal-liquid separation) or partial melting should be considered as viable possibilities to be tested.

Evaluating the cause(s) of Ti, Ta, and Nb (TITAN) enrichment in ocean island basalts using LA-ICP-MS

NASA Astrophysics Data System (ADS)

Lyakov, J.; Durkin, K.; Hirsch, L.; Peters, B.; Hattingh, R.; Day, J. M.

2017-12-01

Titanium, Ta, and Nb (TITAN) enrichments in some ocean island basalt (OIB) lavas have been attributed to mantle source, or to partial melting and fractional crystallization Iprocesses. TITAN anomalies in the mantle sources of OIB would imply these trace elements can be used to track mantle heterogeneity in a manner similar to some isotopic tracers (e.g., He, Os, W), whereas a petrogenetic process to account for TITAN anomalies would be more prosaic. To further evaluate this issue, we have performed laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) of phenocryst phases and matrix on petrographically well-characterized polished-sections of OIB samples. These samples come from five ocean island archipelagos (Canary Islands, the Azores, Samoa, Tubuai'i, Réunion), and are used to assess the citing of Ti, Ta, Nb and associated trace-elements within bulk-rocks. We find poorly-defined but broadly positive correlations between olivine and clinopyroxene modal abundance and Ta/Ta*, Nb/Nb*, but no correlation with Ti/Ti* (where, for example, Ti/Ti* is the primitive mantle normalized ratio, written as: Ti/√[Sm × Tb]). Abundances of olivine and clinopyroxene with samples spanned a wide-range, from 0-70 modal %. We determined trace-element abundances by LA-ICP-MS in a sub-set of samples for major (olivine, clinopyroxene) and minor (e.g., magnetite) phenocryst phases, and for the typically vitrophyric to partly crystallized matrices of samples. Modal reconstruction relative to the bulk rock are broadly similar, although the Ta/Ta*, Nb/Nb* and, especially Ti/Ti* anomalies cannot always be reproduced, especially if Fe-Ti oxide phases were not analyzed due to their limited presence within polished sections. LA-ICP-MS analyses reveal that, while TITAN anomalies are dominantly preserved in the matrix and oxide phases, the role of fractional crystallization of olivine and clinopyroxene is a controlling factor in the magnitude of TITAN anomaly generated. Our results support suggestions that Ti, Ta and Nb are affected by partial melting, assimilation and fractional crystallization processes during magma evolution, generating more prominent TITAN anomalies in volcanic samples than their mantle sources.

Influence of pH and method of crystallization on the solid physical form of indomethacin.

PubMed

Dubbini, Alessandra; Censi, Roberta; Martena, Valentina; Hoti, Ela; Ricciutelli, Massimo; Malaj, Ledjan; Di Martino, Piera

2014-10-01

The purpose of this study was to investigate the effect of pH and method of crystallization on the solid physical form of indomethacin (IDM). IDM, a non steroidal anti-inflammatory drug poorly soluble in water, underwent two different crystallization methods: crystallization by solvent evaporation under reduced pressure at 50.0°C (method A), and crystallization by cooling of solution from 50.0 to 5.0°C (method B). In both cases, several aqueous ethanolic solutions of IDM of different pHs were prepared. pHs were adjusted by adding acidic solutions (HCl 2M) or alkali (NaOH or NH4OH 2M) to an aqueous ethanolic solution of IDM. Thus, several batches were recovered after crystallization. The chemical stability of IDM was verified through (1)H NMR and mass spectroscopy (FIA-ESI-MS), that revealed that IDM degraded in strong alkali media (pH ≥ 12). Crystals obtained under different crystallization conditions at pHs of 1.0, 4.5, 7.0, 8.0, 10.0 and chemically stable were thus characterized for crystal habit by scanning electron microscopy, for thermal behaviour by differential scanning calorimetry, and thermogravimetry, and for solid state by X-ray powder diffractometry. Under the Method A, IDM always crystallized into pure metastable alpha form when solutions were acidified or alkalized respectively with HCl and NH4OH. On the contrary, in presence of NaOH, IDM crystallized under a mixture of alpha and sodium trihydrate form, because the presence of the sodium counter ion orientates the crystallization towards the formation of the trihydrate salt. Under the method B, at pH of 1.0, IDM crystallized under the alpha form; at pH 4.5, IDM crystallized under the form alpha in presence of some nuclei of gamma form; at pH 7.0, 8.0, and 10.0 for NH4OH, IDM crystallized under the most stable polymorph gamma form, whereas in presence of NaOH, a mix of alpha, and salt forms was formed whatever the pH of the solution. Copyright © 2014 Elsevier B.V. All rights reserved.

Crystallization of proteins by dynamic control of supersaturation. Ph.D. Thesis Semiannual Status Report, 21 Mar. - 20 Sep. 1990

NASA Technical Reports Server (NTRS)

Wilson, Lori June

1990-01-01

The growth of protein crystals is known to be the limiting factor in the determination of the three-dimensional structures of most proteins. It is expected that the kinetics of supersaturation, which is directly related to solvent evaporation, will affect protein crystal growth and nucleation and accordingly determine the quality, number, size, and morphology of the crystals. With a technique that controls the evaporation of solvent from a protein solution with N2(g) it is possible to determine the effect of different evaporation profiles on hen egg white lysozyme crystals. Hen egg white lysozyme was chosen as the model protein because it crystallizes easily and has solubility data available for most salt, pH, and temperature ranges. Commercially available lysozyme was further purified by a number of methods. Crystals grown with the purified lysozyme and with the unpurified lysozyme in citrate buffer were different shapes but were found to be of the same symmetry space group by precession photos. Differences were seen in the lysozyme crystals grown using different evaporation rates. At three of the four initial conditions for lysozyme crystal growth, longer evaporation times yielded better crystals. The evaporation times required to see a change in the appearance of the crystals was much longer than expected. The number of rates studied so far represent only a small fraction of the ones now available with the gas evaporation device. The technique also provides for control of both solution pH and temperature which are related to the solubilities of proteins.

Can a fractionally crystallized magma ocean explain the thermo-chemical evolution of Mars?

NASA Astrophysics Data System (ADS)

Plesa, A.-C.; Tosi, N.; Breuer, D.

2014-10-01

The impact heat accumulated during the late stage of planetary accretion can melt a significant part or even the entire mantle of a terrestrial body, giving rise to a global magma ocean. The subsequent cooling of the interior causes the magma ocean to freeze from the core-mantle boundary (CMB) to the surface due to the steeper slope of the mantle adiabat compared to the slope of the solidus. Assuming fractional crystallization of the magma ocean, dense cumulates are produced close to the surface, largely due to iron enrichment in the evolving magma ocean liquid. A gravitationally unstable mantle thus forms, which is prone to overturn. We investigate the cumulate overturn and its influence on the thermal evolution of Mars using mantle convection simulations in 2D cylindrical geometry. We present a suite of simulations using different initial conditions and a strongly temperature-dependent viscosity. We assume that all radiogenic heat sources have been enriched during the freezing-phase of the magma ocean in the uppermost 50 km and that the initial steam-atmosphere created by the degassing of the freezing magma ocean was rapidly lost, implying that the surface temperature is set to present-day values. In this case, a stagnant lid quickly forms on top of the convective interior preventing the uppermost dense cumulates to sink, even when allowing for a plastic yielding mechanism. Below this dense stagnant lid, the mantle chemical gradient settles to a stable configuration. The convection pattern is dominated by small-scale structures, which are difficult to reconcile with the large-scale volcanic features observed over Mars' surface and partial melting ceases in less than 900 Ma. Assuming that the stagnant lid can break because of additional mechanisms and allowing the uppermost dense layer to overturn, a stable density gradient is obtained, with the densest material and the entire amount of heat sources lying above the CMB. This stratification leads to a strong overheating of the lowermost mantle, whose temperature increases to values that exceed the liquidus. The iron-rich melt would most likely remain trapped in the lower part of the mantle. The upper mantle in that scenario cools rapidly and only shows partial melting during the first billion year of evolution. Therefore a fractionated global and deep magma ocean is difficult to reconcile with observations. Different scenarios assuming, for instance, a hemispherical or shallow magma ocean, or a crystallization sequence resulting in a lower density gradient than that implied by pure fractional crystallization will have to be considered.

The petrochemistry of Jake_M: a martian mugearite.

PubMed

Stolper, E M; Baker, M B; Newcombe, M E; Schmidt, M E; Treiman, A H; Cousin, A; Dyar, M D; Fisk, M R; Gellert, R; King, P L; Leshin, L; Maurice, S; McLennan, S M; Minitti, M E; Perrett, G; Rowland, S; Sautter, V; Wiens, R C

2013-09-27

"Jake_M," the first rock analyzed by the Alpha Particle X-ray Spectrometer instrument on the Curiosity rover, differs substantially in chemical composition from other known martian igneous rocks: It is alkaline (>15% normative nepheline) and relatively fractionated. Jake_M is compositionally similar to terrestrial mugearites, a rock type typically found at ocean islands and continental rifts. By analogy with these comparable terrestrial rocks, Jake_M could have been produced by extensive fractional crystallization of a primary alkaline or transitional magma at elevated pressure, with or without elevated water contents. The discovery of Jake_M suggests that alkaline magmas may be more abundant on Mars than on Earth and that Curiosity could encounter even more fractionated alkaline rocks (for example, phonolites and trachytes).

Material limitations on the detection limit in refractometry.

PubMed

Skafte-Pedersen, Peder; Nunes, Pedro S; Xiao, Sanshui; Mortensen, Niels Asger

2009-01-01

We discuss the detection limit for refractometric sensors relying on high-Q optical cavities and show that the ultimate classical detection limit is given by min {Δn} ≳ η, with n + iη being the complex refractive index of the material under refractometric investigation. Taking finite Q factors and filling fractions into account, the detection limit declines. As an example we discuss the fundamental limits of silicon-based high-Q resonators, such as photonic crystal resonators, for sensing in a bio-liquid environment, such as a water buffer. In the transparency window (λ ≳ 1100 nm) of silicon the detection limit becomes almost independent on the filling fraction, while in the visible, the detection limit depends strongly on the filling fraction because the silicon absorbs strongly.

Application of the fractional Fourier transform to the design of LCOS based optical interconnects and fiber switches.

PubMed

Robertson, Brian; Zhang, Zichen; Yang, Haining; Redmond, Maura M; Collings, Neil; Liu, Jinsong; Lin, Ruisheng; Jeziorska-Chapman, Anna M; Moore, John R; Crossland, William A; Chu, D P

2012-04-20

It is shown that reflective liquid crystal on silicon (LCOS) spatial light modulator (SLM) based interconnects or fiber switches that use defocus to reduce crosstalk can be evaluated and optimized using a fractional Fourier transform if certain optical symmetry conditions are met. Theoretically the maximum allowable linear hologram phase error compared to a Fourier switch is increased by a factor of six before the target crosstalk for telecom applications of -40 dB is exceeded. A Gerchberg-Saxton algorithm incorporating a fractional Fourier transform modified for use with a reflective LCOS SLM is used to optimize multi-casting holograms in a prototype telecom switch. Experiments are in close agreement to predicted performance.

Hadean Oceanography: Experimental Constraints on the Development of the Terrestrial Hydrosphere and the Origin of Life on Earth

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

Ryerson, F J

The oxygen isotopic compositions of the world's oldest mineral grains, zircon, have recently been used to infer the compositions of the rocks from which they crystallized. The results appear to require a source that had once experienced isotopic fractionation between clay minerals and liquid water, thereby implying the presence of liquid water at the Earth's surface prior to 4.4 billion years ago, less than 2 million years after accretion. This observation has important implications for the development of the Earth's continental crust. The inferred composition of the zircon source rock is directly dependent upon the oxygen isotopic fractionation between zirconmore » and melt, and zircon and water. These fractionation factors have not been determined experimentally, however, constituting the weak link in this argument. A series of experiments to measure these fractionation factors has been conducted. The experiments consist of finely powdered quartz, a polished single crystal of zircon and isotopically-enriched or isotopically normal water to provide a range of isotopic compositions. The experiments will be run until quartz is in isotopic equilibrium with water. Zircon was expected to partially equilibrate producing an oxygen isotopic diffusion profile perpendicular to the surface. Ion probe spot analysis of quartz and depth profiling of zircon will determine the bulk and surface isotopic compositions of the phases, respectively. The well-known quartz-water isotopic fractionation factors can be used to calculate the oxygen isotopic composition of the fluid, and with the zircon surface composition, the zircon-water fractionation factor. Run at temperatures up to 1000 C for as long as 500 hours have not produced diffusion profiles longer than 50 nm. The steep isotopic gradient at the samples surface precludes use of the diffusion profile for estimation on the surface isotopic composition. The short profiles may be the result of surface dissolution, although such dissolution cannot be resolved in SEM images. The sluggish nature of diffusion in zircon may require that fractionation factors be determined by direct hydrothermal synthesis of zircon rather than by mineral-fluid exchange.« less

Iron Isotope Constraints on Planetesimal Core Formation

NASA Astrophysics Data System (ADS)

Jordan, M.; Young, E. D.

2016-12-01

The prevalence of iron in both planetary cores and silicate mantles renders the element a valuable tool for understanding core formation. Magmatic iron meteorites exhibit an enrichment in 57Fe/54Fe relative to chondrites and HED meteorites. This is suggestive of heavy Fe partitioning into the cores of differentiated bodies. If iron isotope fractionation accompanies core formation, we can elucidate details about the history of accretion for planetary bodies as well as their compositions and relative core sizes. The equilibrium 57Fe/54Fe between metal and silicate is necessary for understanding observed iron isotope compositions and placing constraints on core formation. We measure this fractionation in two Aubrite meteorites, Norton County and Mount Egerton, which have known temperatures of equilibration and equilibrated silicon isotopes. Iron was purified using ion-exchange chromatography. Data were collected on a ThermoFinnigan NeptuneTM multiple-collector inductively coupled plasma-source mass spectrometer (MC-ICP-MS) run in wet plasma mode. The measured fractionation Δ57Femetal-silicate is 0.08‰ ± 0.039 (2 SE) for Norton County and 0.09‰ ± 0.019 (2 SE) for Mount Egerton, indicating that the heavy isotopes of Fe partition into the metallic phase. These rocks are in isotopic equilibrium at a temperature of 1130 K and 1200 K ± 80 K, respectively. The concentration of the heavy isotopes of iron in the metallic phase is consistent with recent experimental studies. Using our measured metal-silicate Fe isotope fractionation and the resulting temperature calibration, while taking into account impurities in the metallic phase and temperatures of equilibration, determine that core formation could explain the observed difference between magmatic iron meteorites and chondrites if parent bodies have small cores. In order to verify that Rayleigh distillation during fractional crystallization was not a cause of iron isotope fractionation in iron meteorites, we measured iron isotope ratios in a suite of iron meteorites representing a large range of degrees of fractional crystallization. We find no clear variation in 57Fe/54Fe among these samples.

Order-disorder-reorder process in thermally treated dolomite samples: a combined powder and single-crystal X-ray diffraction study

NASA Astrophysics Data System (ADS)

Zucchini, A.; Comodi, P.; Katerinopoulou, A.; Balic-Zunic, T.; McCammon, C.; Frondini, F.

2012-04-01

A combined powder and single-crystal X-ray diffraction analysis of dolomite [CaMg(CO3)2] heated to 1,200°C at 3 GPa was made to study the order-disorder-reorder process. The order/disorder transition is inferred to start below 1,100°C, and complete disorder is attained at approximately 1,200°C. Twinned crystals characterized by high internal order were found in samples annealed over 1,100°C, and their fraction was found to increase with temperature. Evidences of twinning domains combined with probable remaining disordered portions of the structure imply that reordering processes occur during the quench. Twin domains are hereby proposed as a witness to thermally induced intra-layer-type cation disordering.

Trace element and petrologic clues to the formation of forsterite-bearing Ca-Al-rich inclusions in the Allende meteorite

NASA Astrophysics Data System (ADS)

Wark, D. A.; Boynton, W. V.; Keays, R. R.; Palme, H.

1987-03-01

This work presents new trace element and petrographic data for three forsterite-bearing, Ca-Al-rich inclusions from the Allende meteorite: TE, 818a, and 110-A. Such inclusions form a continuum with Type B1 and B2 Ca-Al-rich inclusions (CAIs), and the authors refer to them as "Type B3" CAIs. Textures, mineral chemistries, crystal-chemically fractionated REE patterns, and other properties suggest that Type B3 crystallized from partly molten evaporative residues. They also present evidence that 818a was strongly re-heated and modified in the nebula after its initial crystallization: it consists of a core of coarse-grained Ti-Al-pyroxene (Tpx), forsterite, spinel and metal grains and a thick, surrounding mantle of melilite.

Calibration of the QCM/SAW Cascade Impactor for Measurement of Ozone in the Stratosphere

NASA Technical Reports Server (NTRS)

Wright, Cassandra K.; Sims, S. C.; Peterson, C. B.; Morris, V. R.

1997-01-01

The Quartz Crystal Microbalance Surface Acoustic Wave (QCM/SAW) cascade impactor collects size-fractionated distributions of aerosols on a series of 10 MHz quartz crystals and employs SAW devices coated with chemical sensors for gas detection. Presently, we are calibrating the ER-2 certified QCM/SAW cascade impactor in the laboratory for the detection of ozone. Experiments have been performed to characterize the QCM and SAW mass loading, saturation limits, mass frequency relationships, and sensitivity. We are also characterizing sampling efficiency by measuring the loss of ozone on different materials. There are parallel experiments underway to measure the variations in the sensitivity and response of the QCM/SAW crystals as a function of temperature and pressure. Results of the work to date will be shown.

Production, crystallization and X-ray characterization of chemically glycosylated hen egg-white lysozyme

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

López-Jaramillo, F. J., E-mail: javier@lec.ugr.es; Instituto de Biotecnología, Facultad de Ciencias, Universidad de Granada, E-18071; Pérez-Banderas, F.

The feasibility of glycosylation post-purification has been demonstrated by introducing glucose into the model protein lysozyme via a novel reaction that is compatible with biological samples. The crystallization of glycoproteins is one of the challenges to be confronted by the crystallographic community in the frame of what is known as glycobiology. The state of the art for the crystallization of glycoproteins is not promising and removal of the carbohydrate chains is generally suggested since they are flexible and a source of heterogeneity. In this paper, the feasibility of introducing glucose into the model protein hen egg-white lysozyme via a post-purificationmore » glycosylation reaction that may turn any protein into a model glycoprotein whose carbohydrate fraction can be manipulated is demonstrated.« less

The nakhlite meteorites: Augite-rich igneous rocks from Mars

NASA Technical Reports Server (NTRS)

Treiman, Allan H.

2005-01-01

The seven nakhlite meteorites are augite-rich igneous rocks that formed in flows or shallow intrusions of basaltic magma on Mars. They consist of euhedral to subhedral crystals of augite and olivine (to 1 cm long) in fine-grained mesostases. The augite crystals have homogeneous cores of Mg' = 63% and rims that are normally zoned to iron enrichment. The core-rim zoning is cut by iron-enriched zones along fractures and is replaced locally by ferroan low-Ca pyroxene. The core compositions of the olivines vary inversely with the steepness of their rim zoning - sharp rim zoning goes with the most magnesian cores (Mg' = 42%), homogeneous olivines are the most ferroan. The olivine and augite crystals contain multiphase inclusions representing trapped magma. Among the olivine and augite crystals is mesostasis, composed principally of plagioclase and/or glass, with euhedra of titanomagnetite and many minor minerals. Olivine and mesostasis glass are partially replaced by veinlets and patches of iddingsite, a mixture of smectite clays, iron oxy-hydroxides and carbonate minerals. In the mesostasis are rare patches of a salt alteration assemblage: halite, siderite, and anhydrite/ gypsum. The nakhlites are little shocked, but have been affected chemically and biologically by their residence on Earth. Differences among the chemical compositions of the nakhlites can be ascribed mostly to different proportions of augite, olivine, and mesostasis. Compared to common basalts, they are rich in Ca, strongly depleted in Al, and enriched in magmaphile (incompatible) elements, including the LREE. Nakhlites contain little pre-terrestrial organic matter. Oxygen isotope ratios are not terrestrial, and are different in anhydrous silicates and in iddingsite. The alteration assemblages all have heavy oxygen and heavy carbon, while D/H values are extreme and scattered. Igneous sulfur had a solar-system isotopic ratio, but in most minerals was altered to higher and lower values. High precision analyses show mass-independent fractionations of S isotopes. Nitrogen and noble gases are complex and represent three components: two mantle sources (Chas-E and Chas-S), and fractionated Martian atmosphere. The nakhlites are igneous cumulate rocks, formed from basaltic magma at approx.1.3 Ga, containing excess crystals over what would form from pure magma. After accumulation of their augite and olivine crystals, they were affected (to various degrees) by crystallization of the magma, element diffusion among minerals and magma, chemical reactions among minerals and magma, magma movement among the crystals, and post-igneous chemical equilibration. The extent of these modifications varies, from least to greatest, in the order: MIL03346, NWA817, Y000593, Nakhla = Governador Valadares, Lafayette, and NWA998. Chemical, isotopic, and chronologic data confirm that the nakhlites formed on Mars, most likely in thick lava flows or shallow intrusions. Their crystallization ages, referenced to crater count chronologies for Mars, suggest that the nakhlites formed on the large volcanic constructs of Tharsis, Elysium, or Syrtis Major. The nakhlites were suffused with liquid water, probably at approx.620 ma. This water dissolved olivine and mesostasis glass, and deposited iddingsite and salt minerals in their places. The nakhlites were ejected from Mars at approx.10.75Ma by an asteroid impact and fell to Earth within the last 10,000 years. Although the nakhlites are enriched in incompatible elements, their source mantle was strongly depleted. This depletion event was ancient, as the nakhlites source mantle was fractionated while short-lived radionuclides (e.g., t(sub 1/2 = 9 my) were still active. This differentiation event may have been core formation coupled with a magma ocean, as is inferred for the moon.

Cocrystal habit engineering to improve drug dissolution and alter derived powder properties.

PubMed

Serrano, Dolores R; O'Connell, Peter; Paluch, Krzysztof J; Walsh, David; Healy, Anne Marie

2016-05-01

Cocrystallization of sulfadimidine (SDM) with suitable coformers, such as 4-aminosalicylic acid (4-ASA), combined with changes in the crystal habit can favourably alter its physicochemical properties. The aim of this work was to engineer SDM : 4-ASA cocrystals with different habits to investigate the effect on dissolution, and the derived powder properties of flow and compaction. Cocrystals were prepared in a 1 : 1 molar ratio by solvent evaporation using ethanol (habit I) or acetone (habit II), solvent evaporation followed by grinding (habit III) and spray drying (habit IV). Powder X-ray diffraction showed Bragg peak position was the same in all the solid products. The peak intensity varied, indicating different preferred crystal orientation confirmed by SEM micrographs: large prismatic crystals (habit I), large plate-like crystals (habit II), small cube-like crystals (habit III) and microspheres (habit IV). The habit III exhibited the fasted dissolution rate; however, it underwent a polymorphic transition during dissolution. Habits I and IV exhibited the highest Carr's compressibility index, indicating poor flowability. However, habits II and III demonstrated improved flow. Spray drying resulted in cocrystals with improved compaction properties. Even for cocrystals with poor pharmaceutical characteristics, a habit can be engineered to alter the dissolution, flowability and compaction behaviour. © 2015 Royal Pharmaceutical Society.

Effect of milling conditions on solid-state amorphization of glipizide, and characterization and stability of solid forms.

PubMed

Xu, Kailin; Xiong, Xinnuo; Zhai, Yuanming; Wang, Lili; Li, Shanshan; Yan, Jin; Wu, Di; Ma, Xiaoli; Li, Hui

2016-09-10

In this study, the amorphization of glipizide was systematically investigated through high-energy ball milling at different temperatures. The results of solid-state amorphization through milling indicated that glipizide underwent direct crystal-to-glass transformation at 15 and 25°C and crystal-to-glass-to-crystal conversion at 35°C; hence, milling time and temperature had significant effects on the amorphization of glipizide, which should be effectively controlled to obtain totally amorphous glipizide. Solid forms of glipizide were detailedly characterized through analyses of X-ray powder diffraction, morphology, thermal curves, vibrational spectra, and solid-state nuclear magnetic resonance. The physical stability of solid forms was investigated under different levels of relative humidity (RH) at 25°C. Forms I and III are kinetically stable and do not form any new solid-state forms at various RH levels. By contrast, Form II is kinetically unstable, undergoing direct glass-to-crystal transformation when RH levels higher than 32.8%. Therefore, stability investigation indicated that Form II should be stored under relatively dry conditions to prevent rapid crystallization. High temperatures can also induce the solid-state transformation of Form II; the conversion rate increased with increasing temperature. Copyright © 2016 Elsevier B.V. All rights reserved.

Crystallization of tholeiitic basalt in Alae Lava Lake, Hawaii

USGS Publications Warehouse

Peck, D.L.; Wright, T.L.; Moore, J.G.

1966-01-01

The eruption of Kilauea Volcano August 21-23, 1963, left 600,000 cubic meters of basaltic lava in a lava lake as much as 15 meters deep in Alae pit crater. Field studies of the lake began August 27 and include repeated core drilling, measurements of temperature in the crust and melt, and precise level surveys of the lake surface. The last interstitial melt in the lake solidified late in September 1964; by mid August 1965 the maximum temperature was 690??C at a depth of 11.5 meters. Pumice air-quenched from about 1140??C contains only 5 percent crystals - clinopyroxene, cuhedral olivine (Fo 80), and a trace of plagioclase, (An 70). Drill cores taken from the zone of crystallization in the lake show that olivine continued crystallizing to about 1070??C; below that it reacts with the melt, becoming corroded and mantled by pyroxene and plagioclase. Below 1070??C, pyroxene and plagioclase crystallized at a constant ratio. Ilmenite first appeared at about 1070??C and was joined by magnetite at about 1050??C; both increased rapidly in abundance to 1000??C. Apatite first appeared as minute needles in interstitial glass at 1000??C. Both the abundance and index of refraction of glass quenched from melt decreased nearly linearly with falling temperature. At 1070??C the quenched lava contains about 65 percent dark-brown glass with an index of 1.61; at 980??C it contains about 8 percent colorless glass with an index of 1.49. Below 980??C, the percentage of glass remained constant. Progressive crystallization forced exsolution of gases from the melt fraction; these formed vesicles and angular pores, causing expansion of the crystallizing lava and lifting the surface of the central part of the lake an average of 19.5 cm. The solidified basalt underwent pneumatolitic alteration, including deposition of cristobalite at 800??C, reddish alteration of olivine at 700??C, tarnishing of ilmenite at 550??C, deposition of anhydrite at 250??C, and deposition of native sulfur at 100??C. Ferric-ferrous ratios suggest that oxidation with maximum intensity between 550??C and 610??C moved downward in the crust as it cooled; this was followed by reduction at a temperature of about 100??C. The crystallized basalt is a homogeneous fine-grained rock containing on the average 48.3 percent by volume intergranular pyroxene (augite > pigeonite), 34.2 percent plagioclase laths (An60 70), 7.9 percent interstitial glass, 6.9 percent opaques (ilmenite > magnetite), 2.7 percent olivine (Fo70 80), and a trace of apatite. Chemical analyses of 18 samples, ranging from initially quenched pumice to lava cored more than a year after the eruption from the center and from near the base of the lake, show little variation from silica-saturated tholeiitic basalt containing 50.4 percent SiO2, 2.4 percent Na2O, and 0.54 percent K2O. Apparently there was no significant crystal settling and no appreciable vapor-phase transport of these components during the year of crystallization. However, seven samples of interstitial liquid that had been filter-pressed into gash fractures and drill holes from partly crystalline mush near the base of the crust show large differences from the bulk composition of the solidified crust-lower MgO, CaO, and Al2O3; and higher total iron, TiO2, Na2O, K2O, P2O5, and F, and, in most samples, SiO2. The minor elements Ba, Ga, Li, Y, and Yb and possibly Cu tend to be enriched in the filter-pressed liquids, and Cr and possibly Ni tend to be depleted. ?? 1966 Stabilimento Tipografico Francesco Giannini & Figli.

Self-consistent phonon theory of the crystallization and elasticity of attractive hard spheres.

PubMed

Shin, Homin; Schweizer, Kenneth S

2013-02-28

We propose an Einstein-solid, self-consistent phonon theory for the crystal phase of hard spheres that interact via short-range attractions. The approach is first tested against the known behavior of hard spheres, and then applied to homogeneous particles that interact via short-range square well attractions and the Baxter adhesive hard sphere model. Given the crystal symmetry, packing fraction, and strength and range of attractive interactions, an effective harmonic potential experienced by a particle confined to its Wigner-Seitz cell and corresponding mean square vibrational amplitude are self-consistently calculated. The crystal free energy is then computed and, using separate information about the fluid phase free energy, phase diagrams constructed, including a first-order solid-solid phase transition and its associated critical point. The simple theory qualitatively captures all the many distinctive features of the phase diagram (critical and triple point, crystal-fluid re-entrancy, low-density coexistence curve) as a function of attraction range, and overall is in good semi-quantitative agreement with simulation. Knowledge of the particle localization length allows the crystal shear modulus to be estimated based on elementary ideas. Excellent predictions are obtained for the hard sphere crystal. Expanded and condensed face-centered cubic crystals are found to have qualitatively different elastic responses to varying attraction strength or temperature. As temperature increases, the expanded entropic solid stiffens, while the energy-controlled, fully-bonded dense solid softens.

Kinetics of nucleation and crystallization in poly(e-caprolactone) (PCL)

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

Zhuravlev, Evgeny; Schmelzer, Jurn; Wunderlich, Bernhard

2011-01-01

The recently developed differential fast scanning calorimetry (DFSC) is used for a new look at the crystal growth of poly(3-caprolactone) (PCL) from 185 K, below the glass transition temperature, to 330 K, close to the equilibrium melting temperature. The DFSC allows temperature control of the sample and determination of its heat capacity using heating rates from 50 to 50,000 K/s. The crystal nucleation and crystallization halftimes were determined simultaneously. The obtained halftimes cover a range from 3 102 s (nucleation at 215 K) to 3 109 s (crystallization at 185 K). After attempting to analyze the experiments with the classicalmore » nucleation and growth model, developed for systems consisting of small molecules, a new methodology is described which addresses the specific problems of crystallization of flexible linear macromolecules. The key problems which are attempted to be resolved concern the differences between the structures of the various entities identified and their specific role in the mechanism of growth. The structures range from configurations having practically unmeasurable latent heats of ordering (nuclei) to being clearly-recognizable, ordered species with rather sharp disordering endotherms in the temperature range from the glass transition to equilibrium melting for increasingly perfect and larger crystals. The mechanisms and kinetics of growth involve also a detailed understanding of the interaction with the surrounding rigid-amorphous fraction (RAF) in dependence of crystal size and perfection.« less

KREEP basalt petrogenesis: Insights from 15434,181

NASA Astrophysics Data System (ADS)

Cronberger, Karl; Neal, Clive R.

2017-05-01

Returned lunar KREEP basalts originated through impact processes or endogenous melting of the lunar interior. Various methods have been used to distinguish between these two origins, with varying degrees of success. Apollo 15 KREEP basalts are generally considered to be endogenous melts of the lunar interior. For example, sample 15434,181 is reported to have formed by a two-stage cooling process, with large orthopyroxene (Opx) phenocrysts forming first and eventually cocrystalizing with smaller plagioclase crystals. However, major and trace element analyses of Opx and plagioclase coupled with calculated equilibrium liquids are inconsistent with the large orthopyroxenes being a phenocryst phase. Equilibrium liquid rare earth element (REE) profiles are enriched relative to the whole rock (WR) composition, inconsistent with Opx being an early crystallizing phase, and these are distinct from the plagioclase REE equilibrium liquids. Fractional crystallization modeling using the Opx equilibrium liquids as a parental composition cannot reproduce the WR values even with crystallization of late-stage phosphates and zircon. This work concludes that instead of being a phenocryst phase, the large Opx crystals are actually xenocrysts that were subsequently affected by pyroxene overgrowths that formed intergrowths with cocrystallizing plagioclase.

Cortlandtitic enclaves associated with calc-alkaline granites from Tapia-Asturias (Hercynian Belt, northwestern Spain)

NASA Astrophysics Data System (ADS)

Galán, G.; Suárez, O.

1989-10-01

Petrographic and mineralogical characteristics of amphibole-olivine- and pyroxene-bearing ultramafic rocks from Asturias (NW Spain) are dealt with in this paper. These rocks are of cortlandtitic type and occur as small rare enclaves in basic rocks related to Hercynian calc-alkaline, post-tectonic epizonal granites, in the northwest of the Iberian Peninsula. These particular ultramafic enclaves are characterized by poikilitic cumulate microtexture. Olivine (Fo 77-81), spinel, from chromite to pleonaste composition, enstatite, subordinated diopside and sulphides are included in large brown calcic amphibole crystals displaying an irregular zonation. Phlogopite and plagioclase are also found, in a much lower proportion, between the large amphibole crystals. Mineral assemblage and chemical composition of minerals indicate formation conditions of 1150°C, 7-8 kbar of Ptotal and PH 2O < Ptotal. These rocks could represent the earlier products of fractional crystallization from a hydrated high-alumina basalt involved in the genesis of the calc-alkaline granites. This basic magma would start crystallizing at a relatively deep level, carrying up the first products of its crystallization during its ascent.

Crystal Growth and Scintillation Properties of Ce Doped Gd3Ga,Al5O12 Single Crystals

NASA Astrophysics Data System (ADS)

Kamada, Kei; Yanagida, Takayuki; Pejchal, Jan; Nikl, Martin; Endo, Takanori; Tsutsumi, Kousuke; Fujimoto, Yutaka; Fukabori, Akihiro; Yoshikawa, Akira

2012-10-01

Ce1%, 2% and 3% doped Gd3(Ga,Al)5O12 (GAGG) single crystals were grown by the Cz method. Luminescence and scintillation properties were measured. Light yield change along the growth direction and effects of Ce concentration on scintillation properties in Ce:GAGG were studied. Ce3+ 5d-4f emission within 520-530 nm was observed in the Ce:GAGG crystals. The Ce1%:GAGG sample with 3×3×1 mm size showed the highest light yield of 46000 photon/MeV. The energy resolution was 7.8%@662 keV. With increasing solidification fraction, the LY were decreased. It is proposed that the increase of Ga concentration along the growth direction is the main cause of the decrease of LY. The scintillation decay times were accelerated with increasing Ce concentration in the Ce:GAGG crystals. The scintillation decay times were 92.0 ns, 79.1 ns and 68.3 ns in the Ce1, 2 and 3% GAGG, respectively.

Controlling Crystal Microstructure to Minimize Loss in Polymer Dielectrics

NASA Astrophysics Data System (ADS)

Miranda, Daniel; Iacob, Ciprian; Zhang, Shihai; Runt, James

Polymer dielectric films are of great importance for high performance capacitors. For these films it is critical to reduce dielectric loss, as it diminishes efficiency and contributes to waste heat generation during device operation. Here, a model semi-crystalline polymer, poly(ethylene naphthalate) (PEN), was used to examine how morphological factors inhibit chain relaxations responsible for loss. This was achieved by manipulating the extent of crystallization and the crystalline microstructure through a combination of annealing and uniaxial drawing, and investigating their effects on dielectric performance. Varying crystallization conditions influenced the dynamic Tg and extent of rigid amorphous fraction formation, but had a limited effect on loss magnitude. Film orientation however greatly reduced loss, through strain-induced crystallization and development of oriented amorphous mesophasic regions. Post-drawing annealing conditions were capable of further refining the crystal microstructure and, in turn, the dielectric properties. These findings demonstrate that semi-crystalline polymer morphology has a very strong influence on amorphous chain relaxations, and understanding how processing conditions affect morphology is critical to the rational design of polymer dielectrics. Office of Naval Research.

Radical chiral Floquet phases in a periodically driven Kitaev model and beyond

NASA Astrophysics Data System (ADS)

Po, Hoi Chun; Fidkowski, Lukasz; Vishwanath, Ashvin; Potter, Andrew C.

2017-12-01

We theoretically discover a family of nonequilibrium fractional topological phases in which time-periodic driving of a 2D system produces excitations with fractional statistics, and produces chiral quantum channels that propagate a quantized fractional number of qubits along the sample edge during each driving period. These phases share some common features with fractional quantum Hall states, but are sharply distinct dynamical phenomena. Unlike the integer-valued invariant characterizing the equilibrium quantum Hall conductance, these phases are characterized by a dynamical topological invariant that is a square root of a rational number, inspiring the label: radical chiral Floquet phases. We construct solvable models of driven and interacting spin systems with these properties, and identify an unusual bulk-boundary correspondence between the chiral edge dynamics and bulk "anyon time-crystal" order characterized by dynamical transmutation of electric-charge into magnetic-flux excitations in the bulk.

Convective fractionation: A mechanism to provide cryptic zoning (macrosegregation), layering, crescumulates, banded tuffs and explosive volcanism in igneous processes

NASA Astrophysics Data System (ADS)

Rice, Alan

1981-01-01

A large array of igneous and volcanic features has characteristics that are recognized in other disciplines as conclusive and direct evidence of convvection in stratified and/or solidifying melts; e.g., macroscopic segregation (cryptic variation, zoning in magma chambers), mineral layering (in mafic intrusives), crescumulates (fingering) in the vertical and horizontal, banding (in pyroclastics), 'rollover' with attendant flashing of volatiles (explosive volcanism), etc. Some quantitative and qualitative aspect of convection in solidifying and or stratified melts (e.g., mineral layer widths such as are observed inl the Skaergaards) are examined to show consistency with field evidence. Convective fractionation does not possess the physical implausibilities of gravitational segregation (crystal settling). Neither is the field evidence as ambiguous if interpreted in terms of convective fractionation (which can explain amongst other things heavier material overlying lighter). Convective fractionation may operate on larger scales in the interior of planets.

Geochemistry of the Serifos calc-alkaline granodiorite pluton, Greece: constraining the crust and mantle contributions to I-type granitoids

NASA Astrophysics Data System (ADS)

Stouraiti, C.; Baziotis, I.; Asimow, P. D.; Downes, H.

2017-11-01

The Late Miocene (11.6-9.5 Ma) granitoid intrusion on the island of Serifos (Western Cyclades, Aegean Sea) is composed of syn- to post-tectonic granodiorite with quartz monzodiorite enclaves, cut by dacitic and aplitic dikes. The granitoid, a typical I-type metaluminous calcic amphibole-bearing calc-alkaline pluton, intruded the Cycladic Blueschists during thinning of the Aegean plate. Combining field, textural, geochemical and new Sr-Nd-O isotope data presented in this paper, we postulate that the Serifos intrusion is a single-zoned pluton. The central facies has initial 87Sr/86Sr = 0.70906 to 0.7106, ɛNd(t) = - 5.9 to - 7.5 and δ18Οqtz = + 10 to + 10.6‰, whereas the marginal zone (or border facies) has higher initial 87Sr/86Sr = 0.711 to 0.7112, lower ɛ Nd(t) = - 7.3 to - 8.3, and higher δ18Οqtz = + 10.6 to + 11.9‰. The small range in initial Sr and Nd isotopic values throughout the pluton is paired with a remarkable uniformity in trace element patterns, despite a large range in silica contents (58.8 to 72 wt% SiO2). Assimilation of a crustally derived partial melt into the mafic parental magma would progressively add incompatible trace elements and SiO2 to the evolving mafic starting liquid, but the opposite trend, of trace element depletion during magma evolution, is observed in the Serifos granodiorites. Thermodynamic modeling of whole-rock compositions during simple fractional crystallization (FC) or assimilation-fractional crystallization (AFC) processes of major rock-forming minerals—at a variety of pressure, oxidation state, and water activity conditions—fails to reproduce simultaneously the major element and trace element variations among the Serifos granitoids, implying a critical role for minor phases in controlling trace element fractionation. Both saturation of accessory phases such as allanite and titanite (at SiO2 ≥ 71 wt%)(to satisfy trace element constraints) and assimilation of partial melts from a metasedimentary component (to match isotopic data) must have accompanied fractional crystallization of the major phases.

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

Yasuda, Satoshi; Yanagi, Takanori; Yamada, Masafumi D.

Highlights: •Dipolar EPR detects the distance between the spin-labeled kinesin α-1 and α-2 helices. •The distance has at least two populations: 1.5 nm (in crystal form: 20%) and >2.5 nm. •The short distance conformer was populated 40% in the apo state with microtubules. •ATP analog or ADP binding caused the 1.5 nm distance to be less populated (∼20%). •The α-1 helix moves closer to the neck-linker (away from α-2) to facilitate docking. -- Abstract: In kinesin X-ray crystal structures, the N-terminal region of the α-1 helix is adjacent to the adenine ring of the bound nucleotide, while the C-terminal regionmore » of the helix is near the neck-linker (NL). Here, we monitor the displacement of the α-1 helix within a kinesin monomer bound to microtubules (MTs) in the presence or absence of nucleotides using site-directed spin labeling EPR. Kinesin was doubly spin-labeled at the α-1 and α-2 helices, and the resulting EPR spectrum showed dipolar broadening. The inter-helix distance distribution showed that 20% of the spins have a peak characteristic of 1.4–1.7 nm separation, which is similar to what is predicted from the X-ray crystal structure, albeit 80% were beyond the sensitivity limit (>2.5 nm) of the method. Upon MT binding, the fraction of kinesin exhibiting an inter-helix distance of 1.4–1.7 nm in the presence of AMPPNP (a non-hydrolysable ATP analog) and ADP was 20% and 25%, respectively. In the absence of nucleotide, this fraction increased to 40–50%. These nucleotide-induced changes in the fraction of kinesin undergoing displacement of the α-1 helix were found to be related to the fraction in which the NL undocked from the motor core. It is therefore suggested that a shift in the α-1 helix conformational equilibrium occurs upon nucleotide binding and release, and this shift controls NL docking onto the motor core.« less

Trace element diffusion and kinetic fractionation in wet rhyolitic melt

NASA Astrophysics Data System (ADS)

Holycross, Megan E.; Watson, E. Bruce

2018-07-01

Piston-cylinder experiments were run to determine the chemical diffusivities of 21 trace elements (Sc, V, Y, Zr, Nb, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Hf, Th and U) in hydrous rhyolitic melts at 1 GPa pressure and temperatures from 850 to 1250 °C. Diffusion couple glasses were doped with trace elements in low concentrations to characterize the diffusivities of all cations in a single experiment. Laser ablation ICP-MS was used to evaluate the trace element concentration gradients that developed in the silicate glasses. All calculated diffusion coefficients correspond to the temperature dependence D = D0exp(-Ea/RT). Rhyolite liquids contained either ∼4.1 wt% or ∼6.2 wt% dissolved H2O; separate Arrhenius relationships are produced for each melt composition. Trace element diffusivities in the melt with 6.2 wt% H2O are roughly two times higher than those in the less hydrous melt. Calculated trace element diffusion coefficients cover nearly two orders of magnitude at a given temperature. The high field strength elements are the slowest diffusers, followed by the transition metals and heavy rare earth elements. The light rare earth elements have the fastest diffusion rates in hydrous rhyolitic melt. The measured diffusion coefficients range down to values sufficiently low to preclude diffusive homogenization over geochemically realistic time scales in some cases. The substantial differences in the diffusivities of individual cations may result in fractionated trace element signatures in rhyolite melt pockets. A simple model is used to explore the potential for kinetic fractionation of REE during growth of an apatite crystal in a diffusive boundary layer locally saturated in P2O5. The faster-diffusing light REE are more efficiently transported away from the crystal interface than the slower-moving heavy REE. Diffusion effects will enrich the melt boundary layer in slow-moving HREE relative to the faster LREE. The kinetic fractionation of REE in the melt growth medium will result in a precipitated apatite crystal with a disequilibrium trace element composition.

Right ventricular function after coronary artery bypass graft surgery--a magnetic resonance imaging study.

PubMed

Joshi, Subodh B; Roswell, Robert O; Salah, Ali K; Zeman, Peter R; Corso, Paul J; Lindsay, Joseph; Fuisz, Anthon R

2010-01-01

A reduction in right ventricular function commonly occurs in the early postoperative period after coronary artery bypass graft surgery (CABG). We sought to determine the longer-term effect of CABG on right ventricular function. Cardiac magnetic resonance imaging was performed before and approximately 3 months after surgery in 28 patients undergoing elective CABG. Right ventricular (RV) ejection fraction was assessed by planimetry of electrocardiographically gated cine images. There was a statistically significant increase in left ventricular ejection fraction from 50% to 58% (P=.003) after CABG. RV ejection fraction also increased from 54% to 60% (P=.002). In patients with lower baseline RV ejection fraction (below the median, < 53%), this parameter improved from 47% to 57% (P<.001). Both on-pump (47% vs. 62%, P=.003) as well as off-pump CABG (47% vs. 55%, P=.009) lead to an improvement in RV function in patients in the initial low RV ejection fraction group. Long-term right ventricular function was not adversely affected by CABG. An improvement in RV function occurred after surgery in patients with low baseline RV ejection fraction and was similar in patients who underwent surgery with or without cardiopulmonary bypass.

Effects of 1,540-nm Fractional Nonablative Erbium and 2,940-nm Fractional Ablative Erbium on p53 Epidermal Expression After 3 months: A Split-Face Interventional Study.

PubMed

Borges, Juliano; Araújo, Luciana; de Oliveira, Rodrigo P B; Manela-Azulay, Monica

2018-04-16

Expression of p53 by keratinocytes may be important in the pathogenesis of skin cancer induced by ultraviolet light. We used side-by-side nonablative and ablative erbium fractional laser resurfacing to assess the effects on expression of p53 by facial keratinocytes. Ten female patients (age range, 50-63 years) with Fitzpatrick skin Types I-IV and clinical signs of photoaging underwent erbium fractional laser resurfacing (nonablative, 1,540-nm; ablative, 2,940-nm) on opposite sides of the face. Skin biopsies were obtained before treatment and 3 months after treatment for comparison with control biopsies of face and inner arm, quantifying p53 in immunostained tissue sections. Only ablative (2,940-nm) treatments produced a statistically significant reduction in p53 scoring after 3 months. The histologic appearance of skin after ablative resurfacing more closely resembled inner arm skin (rather than facial skin) of control subjects. Epidermal repopulation with p53-negative keratinocytes through ablative erbium fractional laser resurfacing may diminish the risk of eventual malignancy in photoaged skin.

Effect of temperature on the formation of creep substructure in sodium chloride single crystals

NASA Technical Reports Server (NTRS)

Raj, Sai V.; Pharr, George M.

1992-01-01

The effect of temperature on the substructure morphology and the cell and subgrain size was investigated experimentally in NaCl single crystals under creep in the temperature range 573-873 K. It is found that the effect of temperature on the cell and subgrain sizes is weak in comparison with the effect of stress. However, there was a qualitative change in the substructure morphology with temperature, with the cells and subgrains better defined at higher temperatures. The volume fraction of the cell boundaries decreased with increasing temperature, thereby indicating a refinement of the microstructure at higher temperatures.

Calibration of the QCM/SAW Cascade Impactor for Measurement of Ozone

NASA Technical Reports Server (NTRS)

Williams, Cassandra K.; Peterson, C. B.; Morris, V. R.

1997-01-01

The Quartz Crystal Microbalance Surface Acoustic Wave (QCM/SAW) cascade impactor is an instrument designed to collect size-fractionated distributions of aerosols on a series of quartz crystals and employ SAW devices coated with chemical sensors for gas detection. We are calibrating the cascade impactor in our laboratory for future deployment for in-situ experiments to measure ozone. Experiments have been performed to characterize the QCM and SAW mass loading, saturation limits, mass frequency relationships, and sensitivity. The characteristics of mass loading, saturation limits, mass-frequency relationships, sensitivity, and the loss of ozone on different materials have been quantified.

Effect of Ge atoms on crystal structure and optoelectronic properties of hydrogenated Si-Ge films

NASA Astrophysics Data System (ADS)

Li, Tianwei; Zhang, Jianjun; Ma, Ying; Yu, Yunwu; Zhao, Ying

2017-07-01

Optoelectronic and structural properties of hydrogenated microcrystalline silicon-germanium (μc-Si1-xGex:H) alloys prepared by radio-frequency plasma-enhanced chemical vapor deposition (RF-PECVD) were investigated. When the Ge atoms were predominantly incorporated in amorphous matrix, the dark and photo-conductivity decreased due to the reduced crystalline volume fraction of the Si atoms (XSi-Si) and the increased Ge dangling bond density. The photosensitivity decreased monotonously with Ge incorporation under higher hydrogen dilution condition, which was attributed to the increase in both crystallization of Ge and the defect density.

Phase relations of a simulated lunar basalt as a function of oxygen fugacity, and their bearing on the petrogenesis of the Apollo 11 basalts

USGS Publications Warehouse

Tuthill, R.L.; Sato, M.

1970-01-01

A glass of Apollo 11 basalt composition crystallizing at 1 atm at low f{hook}02 showed the following crystallization sequence; ferropseudobrookite at 1210??C, olivine at 1200??C, ilmenite and plagioclase at 1140??C, clinopyroxene at 1113??C. Ferropseudobrookite and olivine have a reaction relation to the melt. This sequence agrees with that assumed on textural grounds for some Apollo 11 basalts. It also indicates that the Apollo 11 basalts cannot have been modified by low-pressure fractionation. ?? 1970.

Febuxostat for the Prevention of Recurrent 2,8-dihydroxyadenine Nephropathy due to Adenine Phosphoribosyltransferase Deficiency Following Kidney Transplantation

PubMed Central

Nanmoku, Koji; Kurosawa, Akira; Shinzato, Takahiro; Shimizu, Toshihiro; Kimura, Takaaki; Yagisawa, Takashi

2017-01-01

Adenine phosphoribosyltransferase (APRT) deficiency is a rare autosomal recessive disorder that results in irreversible renal damage due to 2,8-dihydroxyadenine (DHA) nephropathy. A 28-year-old man underwent living-related kidney transplantation for chronic kidney disease of unknown etiology. Numerous spherical brownish crystals observed in his urinary sediment on postoperative day 3 and were observed within the tubular lumen of renal allograft biopsy specimens on postoperative day 7. After a genetic diagnosis, febuxostat treatment was started on postoperative day 7, with the dosage gradually increased to 80 mg/day until complete the disappearance of 2,8-DHA crystals. Febuxostat prevented secondary 2,8-DHA nephropathy after kidney transplantation. PMID:28566603

Crystal structure and phase transitions of sodium potassium niobate perovskites

NASA Astrophysics Data System (ADS)

Tellier, J.; Malic, B.; Dkhil, B.; Jenko, D.; Cilensek, J.; Kosec, M.

2009-02-01

This paper presents the crystal structure and the phase transitions of K xNa 1- xNbO 3 (0.4 ≤ x ≤ 0.6). X-ray diffraction measurements were used to follow the change of the unit-cell parameters and the symmetry in the temperature range 100-800 K. At room temperature all the compositions exhibited a monoclinic metric of the unit cell with a small monoclinic distortion (90.32° ≤ β ≤ 90.34°). No major change of symmetry was evidenced in the investigated compositional range, which should be characteristic of the morphotropic phase-boundary region. With increasing temperature, the samples underwent first-order monoclinic-tetragonal and tetragonal-cubic transitions. Only the potassium-rich phases were rhombohedral at 100 K.

An experimental and numerical study of the light scattering properties of ice crystals with black carbon inclusions

NASA Astrophysics Data System (ADS)

Arienti, Marco; Geier, Manfred; Yang, Xiaoyuan; Orcutt, John; Zenker, Jake; Brooks, Sarah D.

2018-05-01

We investigate the optical properties of ice crystals nucleated on atmospheric black carbon (BC). The parameters examined in this study are the shape of the ice crystal, the volume fraction of the BC inclusion, and its location inside the crystal. We report on new spectrometer measurements of forward scattering and backward polarization from ice crystals nucleated on BC particles and grown under laboratory-controlled conditions. Data from the Cloud and Aerosol Spectrometer with Polarization (CASPOL) are used for direct comparison with single-particle calculations of the scattering phase matrix. Geometrical optics and discrete dipole approximation techniques are jointly used to provide the best compromise of flexibility and accuracy over a broad range of size parameters. Together with the interpretation of the trends revealed by the CASPOL measurements, the numerical results confirm previous reports on absorption cross-section magnification in the visible light range. Even taking into account effects of crystal shape and inclusion position, the ratio between absorption cross-section of the compound particle and the absorption cross-section of the BC inclusion alone (the absorption magnification) has a lower bound of 1.5; this value increases to 1.7 if the inclusion is centered with respect to the crystal. The simple model of BC-ice particle presented here also offers new insights on the effect of the relative position of the BC inclusion with respect to the crystal's outer surfaces, the shape of the crystal, and its size.

FCC-HCP coexistence in dense thermo-responsive microgel crystals

NASA Astrophysics Data System (ADS)

Karthickeyan, D.; Joshi, R. G.; Tata, B. V. R.

2017-06-01

Analogous to hard-sphere suspensions, monodisperse thermo-responsive poly (N-isopropyl acrylamide) (PNIPAM) microgel particles beyond a volume fraction (ϕ) of 0.5 freeze into face centered cubic (FCC)-hexagonal close packed (HCP) coexistence under as prepared conditions and into an FCC structure upon annealing. We report here FCC-HCP coexistence to be stable in dense PNIPAM microgel crystals (ϕ > 0.74) with particles in their deswollen state (referred to as osmotically compressed microgel crystals) and the FCC structure with particles in their swollen state by performing annealing studies with different cooling rates. The structure of PNIPAM microgel crystals is characterized using static light scattering technique and UV-Visible spectroscopy and dynamics by dynamic light scattering (DLS). DLS studies reveal that the particle motion is diffusive at short times in crystals with ϕ < 0.74 and sub-diffusive at short times in PNIPAM crystals with ϕ > 0.74. The observed sub-diffusive behavior at short times is due to the overlap (interpenetration) of the dangling polymer chains between the shells of neighbouring PNIPAM microgel particles. Overlap is found to disappear upon heating the crystals well above their melting temperature, Tm due to reduction in the particle size. Annealing studies confirm that the overlap of dangling polymer chains between the shells of neighbouring PNIPAM spheres is responsible for the stability of FCC-HCP coexistence observed in osmotically compressed PNIPAM microgel crystals. Results are discussed in the light of recent reports of stabilizing the HCP structure in hard sphere crystals by adding interacting polymer chains.

Polymorphic Crystallization and Crystalline Reorganization of Poly(l-lactic acid)/Poly(d-lactic acid) Racemic Mixture Influenced by Blending with Poly(vinylidene fluoride).

PubMed

Yu, Chengtao; Han, Lili; Bao, Jianna; Shan, Guorong; Bao, Yongzhong; Pan, Pengju

2016-08-18

The effects of poly(vinylidene fluoride) (PVDF) on the crystallization kinetics, competing formations of homocrystallites (HCs) and stereocomplexes (SCs), polymorphic crystalline structure, and HC-to-SC crystalline reorganization of the poly(l-lactic acid)/poly(d-lactic acid) (PLLA/PDLA) racemic mixture were investigated. Even though the PLLA/PDLA/PVDF blends are immiscible, blending with PVDF enhances the crystallization rate and SC formation of PLLA/PDLA components at different temperatures that are higher or lower than the melting temperature of the PVDF component; it also facilitates the HC-to-SC melt reorganization upon heating. The crystallization rate and degree of SC crystallinity (Xc,SC) of PLLA/PDLA components in nonisothermal crystallization increase after immiscible blending with PVDF. At different isothermal crystallization temperatures, the crystallization half-time of PLLA/PDLA components decreases; its spherulitic growth rate and Xc,SC increase as the mass fraction of PVDF increases from 0 to 0.5 in the presence of either a solidified or a molten PVDF phase. The HCs formed in primary crystallization of PLLA/PDLA components melt and recrystallize into SCs upon heating; the HC-to-SC melt reorganization is promoted after blending with PVDF. We proposed that the PVDF-promoted crystallization, SC formation, and HC-to-SC melt reorganization of PLLA/PDLA components in PLLA/PDLA/PVDF blends stem from the enhanced diffusion ability of PLLA and PDLA chains.

Origin of temporal compositional trends in monogenetic vent eruptions: Insights from the crystal cargo in the Papoose Canyon sequence, Big Pine Volcanic Field, CA

NASA Astrophysics Data System (ADS)

Gao, Ruohan; Lassiter, John C.; Ramirez, Gabrielle

2017-01-01

Many monogenetic vents display systematic temporal-compositional variations over the course of eruption. Previous studies have proposed that these trends may reflect variable degrees of crustal assimilation, or melting and mixing of heterogeneous mantle source(s). Discrimination between these two endmember hypotheses is critical for understanding the plumbing systems of monogenetic volcanoes, which pose a significant volcanic hazard in many areas. In this study, we examine the Papoose Canyon (PC) monogenetic vent in the Big Pine Volcanic Field (BPVF), which had been well characterized for temporal-compositional variations in erupted basalts. We present new major and trace element and Sr-Nd-Pb-O isotopic data from the PC "crystal cargo" (phenocrysts and xenoliths). Comparison of "crystal cargo" and host basalt provides new constraints on the history of magma storage, fractionation, and crustal contamination that are obscured in the bulk basalts due to pre- and syn-eruptive magma mixing processes. The abundances of phenocrysts and ultramafic xenoliths in the PC sequence decrease up-section. Olivine and clinopyroxene phenocrysts span a wide range of Mg# (77-89). The majority of phenocrysts are more evolved than olivine or clinopyroxene in equilibrium with their host basalts (Mg# = 68- 71, equilibrium Fo ≈ 85- 89). In addition, the ultramafic xenoliths display cumulate textures. Olivine and clinopyroxene from ultramafic xenoliths have Mg# (73-87) similar to the phenocrysts, and lower than typical mantle peridotites. Sr-Nd-Pb isotope compositions of the xenoliths are similar to early PC basalts. Finally, many clinopyroxene phenocrysts and clinopyroxene in xenoliths have trace element abundances in equilibrium with melts that are more enriched than the erupted basalts. These features suggest that the phenocrysts and xenoliths derive from melt that is more fractionated and enriched than erupted PC basalts. Pressure constraints suggest phenocrysts and ultramafic xenoliths crystallized at ∼5-7 kbar, corresponding to mid-crust depths. Correlations between HFSE depletion and Sr-Nd-Pb isotopic compositions, high δ18 O values in olivines, and radiogenic Os isotopic compositions in whole rocks also suggest incorporation of a crustally contaminated component. We propose that the phenocrysts and ultramafic xenoliths derive from melts that ponded and fractionated and assimilated continental crust, possibly in mid-crustal sills. These melts were drained and mixed with more primitive melts as the eruption began, and the temporal-compositional trends and decreasing crystal phase abundances reflect gradual deflation and exhaustion of these sills as the eruption progressed. The isotopic variations in the PC sequence span much of the compositional range observed in the BPVF. Evidence for variable crustal contamination of PC basalts suggests that much of the isotopic variation observed in the BPVF may also reflect crustal contamination rather than mantle source heterogeneity as previously proposed. In addition, evidence of pre-eruptive magma ponding and fractionation, if applicable to other monogenetic vents, may have significant implications for monitoring and hazard assessment of monogenetic volcano fields.

Petrology of the 1877 eruption of Cotopaxi Volcano, Ecuador: Insight on magma evolution and storage

NASA Astrophysics Data System (ADS)

Saalfeld, M. A.; Panter, K. S.; Kelley, D.

2017-12-01

Cotopaxi is a stratovolcano in the Northern Andes Volcanic Zone, and has a history of bimodal volcanism, alternating between rhyolite and andesite. With Cotopaxi reawakening in 2015 after 100 years of quiescence, the question of what is occurring beneath the surface becomes especially poignant. To answer this question, we must look to the volcano's past. This work characterizes the mineralogy and geochemistry of the recent eruptive products of Cotopaxi, with emphasis on the two pulses of the 1877 eruption. Additionally, pressure and temperature are estimated for magmas prior to eruption. This will allow a better understanding of the magma plumbing system and its evolution over time. Over the past 500 years Cotopaxi has had five major eruptive events (VEI 3-4), which occurred in 1532, 1742, 1744, 1768, and 1877, and included pyroclastic surges, scoria flows, and lahars. After the initial pulse of the 1877 eruption and the subsequent lahars, a second pulse of magma produced a pyroclastic density current containing scoria clasts up to 1 meter in diameter. All samples are basaltic andesite to andesite (56-59 wt. % SiO2), and a mineral assemblage of pl + opx + cpx + mag ± ol. Plagioclase range from An47 to An78 and show both normal and reverse zoning. Normally zoned crystals exhibit greater compositional variation between cores and rims than reversely zoned crystals (median Ancore-Anrim 8% vs 4%, respectively), indicating that crystal fractionation is a dominant process but that mixing also played a role in magma genesis. Pyroxenes occur as augite and enstatite and do not exhibit significant zoning. The similar petrology of these eruptions suggests that they were part of a relatively long-lived system that underwent differentiation and replenishment between eruptions. Thermobarometric data indicate that magma storage occurred at temperatures of 1100-1150°C and pressures ranging from 2 kbar (during the 1877 eruption) to 4 kbar (during the 1742 eruption), which is equivalent to depths of 7 and 14 km, respectively. Geodetic and seismic data from Hickey et al. (2015) indicate that magma is currently being stored at a depth of 4-5 km. While thermobarometry is poorly constrained, it suggests magma storage has become progressively shallower over time. Hickey et al. (2015), J. Geophys. Res. Solid Earth 120, 1473-1486.

A Chondrule from the Mokoia (CV3) Chondrite with Anomalously Low 26Mg*: Evidence for a Multi-Stage History-

NASA Astrophysics Data System (ADS)

Claydon, J. L.; Elliott, T.; Coath, C. D.; Chen, H. W.; Taylor, C. A.; Russell, S. S.

2015-07-01

MC-ICP-MS measurements of Mg isotopes in chondrule MOK13B reveal that it may have formed from low-Al/Mg material that underwent chemical fractionation to increase Al/Mg after decay of 26-Al, or it may sample a region with anomalous Al or Mg isotopes.

Evolution of the Campanian Ignimbrite Magmatic System I: Constraints on Compositional Zonation and Eruption Probability Imposed By Phase Equilibria

NASA Astrophysics Data System (ADS)

Fowler, S.; Spera, F.; Bohrson, W.; Belkin, H.; Devivo, B.

2005-12-01

The eruption and deposition of the ~39.3 ka Campanian Ignimbrite (CI), a large volume (~200 km3 DRE) trachytic to phonolitic ignimbrite, is the dominant event in the history of the Campi Flegrei volcanic field near Naples, Italy. In an effort to comprehend its petrological evolution, we have conducted ~~110 MELTS (Ghiorso, 1997) phase equilibria simulations of the major element evolution of parental CI magma. The goals of this work are to approximate oxygen fugacity (fO2), initial dissolved water content and pressure at which isobaric closed system fractional crystallization of parental melt most accurately captures the observed liquid line of descent and to study the implications of heat extraction from parental CI magma with respect to the origin of compositional zonation and the probability of explosive eruption. Although the CI magma body did not evolve as a perfectly closed system, this assumption allows quantitative insight into magma-host rock mass exchange using trace element and isotopic data (see companion contribution by Bohrson et al.). The parental melt composition was reconstructed using data for melt inclusions trapped within CI clinopyroxene phenocrysts reported by Webster et al. (2003), while allowing for reaction between parental melt and clinopyroxene host. The inferred parental melt is a basaltic trachyandesite. The search space for pressure, (fO2) and initial dissolved H2O was 0.1-0.5 in 0.05 GPa increments, QFM-1 to QFM+3 and 1, 2 and 3 wt. % H2O, respectively. The criteria used to judge the quality of a simulation include correspondence of the MELTS prediction with CI liquid and phenocryst compositions. Results indicate that a good first-order model involves evolution from a basaltic trachyandesite parent by isobaric (~0.15 GPa) crystal fractionation initially containing ~3 wt% dissolved H2O along the QFM+1 buffer. H2O first saturates at 1127°C at 0.15 GPa when the dissolved water content is ~4 wt %. A striking result is the discovery of a pseudo-invariant point at ~883°C (Tip) and 0.15 GPa. The fraction of melt changes abruptly from ~0.5 to ~0.1 at Tip due to the simultaneous crystallization of alkali feldspar, plagioclase, spinel, biotite and apatite. At Tip, there is a dramatic decrease in the viscosity of melt (by a factor of four) and magma density (~5%) and an increase in the dissolved H2O content of the melt (from 4.4-5.1 wt%) and in the volume fraction,θ, of supercritical fluid in the multiphase system. In particular, θ increases from ~0.05 at 885°C to ~0.6 at 882°C. The liquid composition also changes discontinuously at Tip with Si, Na, and H2O increasing and K and Al decreasing as temperature falls below Tip. The marked variations in composition and properties of volatile-saturated melt and magma were the trigger that led to the catastrophic eruption and formation of the compositionally-zoned CI magma. Because phase equilibria modeling provides information on the enthalpy changes associated with fractional crystallization and because the dimensions of the CI magma chamber and heat extraction rate can be approximated, a time scale for CI magmatic evolution can be derived. The estimated crystallization duration (τ) is10-100 ka and 75% of τ is spent at or near Tip.

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.

Ablative Fractional Carbon Dioxide Laser in the Treatment of Chronic, Posttraumatic, Lower-Extremity Ulcers in Elderly Patients.

PubMed

Phillips, Tania J; Morton, Laurel M; Uebelhoer, Nathan S; Dover, Jeffrey S

2015-08-01

Treating posttraumatic lower extremity wounds can be challenging, especially in elderly patients. Recently, the use of fractional carbon dioxide laser has been shown to improve wound healing in scar-related wounds. We used this treatment modality in posttraumatic wounds that were slow to heal in 3 elderly patients. Each wound underwent one fractional carbon dioxide laser treatment. The wound base was treated at 30 mJ and 5% density. The entire wound edge and 1 to 2 cm into the normal surrounding skin were treated at 50 mJ and 5% density. One pass was completed at 150 Hz per treatment. Treatments were well tolerated with only mild discomfort. Each wound healed by 60% or greater within 3 weeks. No adverse events were reported aside from mild and transient erythema at site of treatment. Fractional carbon dioxide laser treatment appeared to accelerate healing in each of these posttraumatic wounds. It may be a helpful adjunct in nonhealing posttraumatic wounds.

Record of Fluctuating Magmatic Environments, Melt Fractionation, and Mixing of Crystals: Elemental Compositions of Zircon Zones, Spirit Mountain Batholith, Nevada

NASA Astrophysics Data System (ADS)

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

2006-12-01

Spirit Mountain batholith is a large, tilted, subvolcanic intrusion in southernmost Nevada (Walker et al., in press; Lowery Claiborne et al., in press). Field relations and elemental chemistry of rocks ranging from felsic cumulates to leucogranites demonstrate both fractionation and frequent recharging. SHRIMP U-Pb analysis of zircon reveals a 2 m.y. history (17.4-15.3 Ma) for the batholith; almost all of the samples record multiple age populations. Elemental concentrations and zoning patterns document the utility of zircon in tracking magmatic environments and crystal transfer processes and provide important insights into the complex and protracted history of the batholith. The data lend strong support to the Watson et al. (2006) Ti-in-zircon thermometer. At reasonable a(TiO2) between 0.5 and 0.9, all calculated T's are consistent with petrological constraints and granite phase equilibria; using a(TiO2) = 0.7, T ranges from 675-900 C. Over this apparent T interval, which reflects a range in Ti from 3.2-34 ppm, concentrations of Hf (6000-18000 ppm), U (20-5000 ppm), and Th (50-13,000 ppm), and REE patterns all vary dramatically and systematically. Hf, U, Th, and Ce/Ce* are negatively correlated with T; LREE/MREE, MREE/HREE, and Eu/Eu* are positively correlated with T. These variations indicate that zircon preferentially incorporated Zr over Hf (hence falling Zr/Hf); U and Th behaved as strongly incompatible elements in the crystallizing assemblage as a whole; compatibility of REE increased with decreasing atomic number (effect of LREE accessories?); Eu+2 was more compatible (feldspars) and Ce+4 less compatible than equivalent +3 REE. All of these trends are consistent with the observed crystallizing assemblage and with general trends in whole rocks. More striking, however, is intrasample and intragrain variability. Although leucogranite samples have a larger proportion of zircon with compositions indicating low T and growth from fractionated melt, all samples have a very wide, and overlapping, range of zircon compositions. Many grains are very strongly zoned, and some individual grains show almost the full range of calculated T and elemental composition. Rims of zircons from the leucogranites are typically "cold" and evolved, but many have high-T interiors that contrast with host rock. Core-to-rim zoning is commonly not monotonic but rather strongly fluctuating, indicating that during growth zircon experienced episodes of increased T and immersion in less evolved melts. These patterns of compositional variability reveal that zircons survived heating events; were entrained in ascending fractionated melt; and were exchanged among contrasting magma batches. Such a history is consistent with protracted residence in a large, multiply replenished and rejuvenated mushy magma system in which melt fraction fluctuated in space and time.

Nd Isotope and U-Th-Pb Age Mapping of Single Monazite Grains by Laser Ablation Split Stream Analysis

NASA Astrophysics Data System (ADS)

Fisher, C. M.; Hanchar, J. M.; Miller, C. F.; Phillips, S.; Vervoort, J. D.; Martin, W.

2015-12-01

Monazite is a common accessory mineral that occurs in medium to high grade metamorphic and Ca-poor felsic igneous rocks, and often controls the LREE budget (including Sm and Nd) of the host rock in which it crystallizes. Moreover, it contains appreciable U and Th, making it an ideal mineral for determining U-Th-Pb ages and Sm-Nd isotopic compositions, both of which are readily determined using in situ techniques with very high spatial resolution like LA-MC-ICPMS. Here, we present the results of laser ablation split stream analyses (LASS), which allows for simultaneous determination of the age and initial Nd isotopic composition in a single analysis. Analyses were done using a 20mm laser spot that allowed for detailed Nd isotope mapping of monazite grains (~30 analyses per ~250mm sized grain). Combined with LREE ratios (e.g., Sm/Nd, Ce/Gd, and Eu anomalies) these results yield important petrogenetic constraints on the evolution of peraluminous granites from the Old Woman-Piute batholith in southeastern California. Our findings also allow an improved understanding of the causes of isotope heterogeneity in granitic rocks. U-Th-Pb age mapping across the crystals reveals a single Cretaceous age for all grains with precision and accuracy typical of laser ablation analyses (~2%). In contrast, the concurrent Nd isotope mapping yields homogeneous initial Nd isotope compositions for some grains and large initial intra-grain variations of up to 8 epsilon units in others. The grains that yield homogeneous Nd isotope compositions have REE ratios suggesting that they crystallized in a fractionally crystallizing magma. Conversely, other grains, which also record fractional crystallization of both feldspar and LREE rich minerals, demonstrate a change in the Nd isotope composition of the magma during crystallization of monazite. Comparison of inter- and intra-grain Nd isotope compositions reveals further details on the potential mechanisms responsible for isotope heterogeneity present in single rock samples. This method highlights the potential of single grain isotope mapping of LREE phases such as monazite, allanite, and titanite for understanding both igneous and metamorphic petrogenesis.

The U-Th-Pb, Sm-Nd, and Ar-Ar isotopic systematics of lunar meteorite Yamato-793169

NASA Technical Reports Server (NTRS)

Torigoye, Noriko; Misawa, Keji; Dalrymple, G. Brent; Tatsumoto, Mitsunobu

1993-01-01

U-Th-Pb, Sm-Nd, and (Ar-40)-(Ar-39) isotopic studies were performed on Yamato (Y)-793169, an unbrecciated diabasic lunar meteorite whose chemical composition is close to low Ti(LT) and very low-Ti (VLT) mare basalts. The isotopic data indicate that the meteorite was formed earlier than 3.9 Ga from a source with low U/Pb and high Sm/Nd and was distributed by a thermal event at 751 Ma. due to the small sample size (104 mg), a plagioclase crystal and glass grains were handpicked for Ar analysis, leaving four fractions for the U-Th-Pb and Sm-Nd studies; a fine-grained fraction (less than 63 microns; Fine) and three medium-grained fractions (63-150 microns). Medium-grained fractions were divided by density; a heavy fraction (rho greater than 3.3) consisting mainly of pyroxene (PX1), a lighter fraction (rho less than 2.8) consisting of plagioclase (PL), and a middle density fraction (predominantly pyroxene; PX2). The fractions were washed with acetone and alcohol, and then leached in 0.01 HBr and 0.1N HBr in order to remove any terrestrial Pb contamination. Analysis of the HBr leaches revealed that this meteorite was heavily contaminated with terrestrial Pb during its residence in Antarctic ice.

Krypton ion irradiation-induced amorphization and nano-crystal formation in pyrochlore Lu2Ti2O7 at room temperature

NASA Astrophysics Data System (ADS)

Xie, Qiu-Rong; Zhang, Jian; Yin, Dong-Min; Guo, Qi-Xun; Li, Ning

2015-12-01

Polycrystalline pyrochlore Lu2Ti2O7 pellets are irradiated with 600-keV Kr3+ ions up to a fluence of 1.45 × 1016 Kr3+/cm2. Irradiation induced structural modifications are examined by using grazing incidence x-ray diffraction (GIXRD) and cross-sectional transmission electron microscopy (TEM). The GIXRD reveals that amorphous fraction increases with the increase of fluences up to 2 × 1015 Kr3+/cm2, and the results are explained with a direct-impact model. However, when the irradiation fluence is higher than 2 × 1015 Kr3+/cm2, the amorphous fraction reaches a saturation of ∼80%. Further TEM observations imply that nano-crystal is formed with a diameter of ∼10 nm within the irradiation layer at a fluence of 4 × 1015 Kr3+/cm2. No full amorphization is achieved even at the highest fluence of 1.45 × 1016 Kr3+/cm2 (∼36 displacement per atom). The high irradiation resistance of pyrochlore Lu2Ti2O7 at higher fluence is explained on the basis of enhanced radiation tolerance of nano-crystal structure. Project sponsored by the National Natural Science Foundation of China (Grant No. 11205128) and the Fundamental Research Funds for the Central Universities, China (Grant No. 2012121034).

Carbonate substitution in the mineral component of bone: Discriminating the structural changes, simultaneously imposed by carbonate in A and B sites of apatite

NASA Astrophysics Data System (ADS)

Madupalli, Honey; Pavan, Barbara; Tecklenburg, Mary M. J.

2017-11-01

The mineral component of bone and other biological calcifications is primarily a carbonate substituted calcium apatite. Integration of carbonate into two sites, substitution for phosphate (B-type carbonate) and substitution for hydroxide (A-type carbonate), influences the crystal properties which relate to the functional properties of bone. In the present work, a series of AB-type carbonated apatites (AB-CAp) having varying A-type and B-type carbonate weight fractions were prepared and analyzed by Fourier transform infrared spectroscopy (FTIR), powder X-ray diffraction (XRD), and carbonate analysis. A detailed characterization of A-site and B-site carbonate assignment in the FTIR ν3 region is proposed. The mass fractions of carbonate in A-site and B-site of AB-CAp correlate differently with crystal axis length and crystallite domain size. In this series of samples reduction in crystal domain size correlates only with A-type carbonate which indicates that carbonate in the A-site is more disruptive to the apatite structure than carbonate in the B-site. High temperature methods were required to produce significant A-type carbonation of apatite, indicating a higher energy barrier for the formation of A-type carbonate than for B-type carbonate. This is consistent with the dominance of B-type carbonate substitution in low temperature synthetic and biological apatites.

Structure of finite sphere packings via exact enumeration: Implications for colloidal crystal nucleation

NASA Astrophysics Data System (ADS)

Hoy, Robert S.; Harwayne-Gidansky, Jared; O'Hern, Corey S.

2012-05-01

We analyze the geometric structure and mechanical stability of a complete set of isostatic and hyperstatic sphere packings obtained via exact enumeration. The number of nonisomorphic isostatic packings grows exponentially with the number of spheres N, and their diversity of structure and symmetry increases with increasing N and decreases with increasing hyperstaticity H≡Nc-NISO, where Nc is the number of pair contacts and NISO=3N-6. Maximally contacting packings are in general neither the densest nor the most symmetric. Analyses of local structure show that the fraction f of nuclei with order compatible with the bulk (rhcp) crystal decreases sharply with increasing N due to a high propensity for stacking faults, five- and near-fivefold symmetric structures, and other motifs that preclude rhcp order. While f increases with increasing H, a significant fraction of hyperstatic nuclei for N as small as 11 retain non-rhcp structure. Classical theories of nucleation that consider only spherical nuclei, or only nuclei with the same ordering as the bulk crystal, cannot capture such effects. Our results provide an explanation for the failure of classical nucleation theory for hard-sphere systems of N≲10 particles; we argue that in this size regime, it is essential to consider nuclei of unconstrained geometry. Our results are also applicable to understanding kinetic arrest and jamming in systems that interact via hard-core-like repulsive and short-ranged attractive interactions.

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.

A liquid-liquid transition in supercooled aqueous solution related to the HDA-LDA transition.

PubMed

Woutersen, Sander; Ensing, Bernd; Hilbers, Michiel; Zhao, Zuofeng; Angell, C Austen

2018-03-09

Simulations and theory suggest that the thermodynamic anomalies of water may be related to a phase transition between two supercooled liquid states, but so far this phase transition has not been observed experimentally because of preemptive ice crystallization. We used calorimetry, infrared spectroscopy, and molecular dynamics simulations to investigate a water-rich hydrazinium trifluoroacetate solution in which the local hydrogen bond structure surrounding a water molecule resembles that in neat water at elevated pressure, but which does not crystallize upon cooling. Instead, this solution underwent a sharp, reversible phase transition between two homogeneous liquid states. The hydrogen-bond structures of these two states are similar to those established for high- and low-density amorphous (HDA and LDA) water. Such structural similarity supports theories that predict a similar sharp transition in pure water under pressure if ice crystallization could be suppressed. Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

Effects of heavy-ion irradiation on the microwave surface impedance of (Ba1-x K x )Fe2As2 single crystals

NASA Astrophysics Data System (ADS)

Ghigo, G.; Torsello, D.; Gerbaldo, R.; Gozzelino, L.; Laviano, F.; Tamegai, T.

2018-07-01

The electrodynamic response of Ba1-x K x Fe2As2 single crystals at the microwave frequencies has been investigated by means of a coplanar resonator technique, at different values of non-magnetic disorder introduced into the samples by heavy-ion irradiation. The surface impedance Z s = R s + iX s conforms to the classical skin effect above the critical temperature. Below T c, R s monotonically decreases while X s shows a peak, which evolves as a function of the irradiation fluence. The disorder-dependent Z s (T) curves are analyzed within a two-fluid model, suitably modified to account for a finite quasiparticle fraction at T = 0. The analysis gives, for the unirradiated crystal, quasiparticle relaxation times τ that are in good agreement with previous literature. Smaller τ values are deduced for the disordered crystals, both in the normal and in the superconducting states. The limits of application of the model are discussed.

Phase equilibria in the lysozyme-ammonium sulfate-water system.

PubMed

Moretti, J J; Sandler, S I; Lenhoff, A M

2000-12-05

Ternary phase diagrams were measured for lysozyme in ammonium sulfate solutions at pH values of 4 and 8. Lysozyme, ammonium sulfate, and water mass fractions were assayed independently by UV spectroscopy, barium chloride titration, and lyophilization respectively, with mass balances satisfied to within 1%. Protein crystals, flocs, and gels were obtained in different regions of the phase diagrams, and in some cases growth of crystals from the gel phase or from the supernatant after floc removal was observed. These observations, as well as a discontinuity in protein solubility between amorphous floc precipitate and crystal phases, indicate that the crystal phase is the true equilibrium state. The ammonium sulfate was generally found to partition unequally between the supernatant and the dense phase, in disagreement with an assumption often made in protein phase equilibrium studies. The results demonstrate the potential richness of protein phase diagrams as well as the uncertainties resulting from slow equilibration. Copyright 2000 John Wiley & Sons, Inc.

Acoustic Injectors for Drop-On-Demand Serial Femtosecond Crystallography.

PubMed

Roessler, Christian G; Agarwal, Rakhi; Allaire, Marc; Alonso-Mori, Roberto; Andi, Babak; Bachega, José F R; Bommer, Martin; Brewster, Aaron S; Browne, Michael C; Chatterjee, Ruchira; Cho, Eunsun; Cohen, Aina E; Cowan, Matthew; Datwani, Sammy; Davidson, Victor L; Defever, Jim; Eaton, Brent; Ellson, Richard; Feng, Yiping; Ghislain, Lucien P; Glownia, James M; Han, Guangye; Hattne, Johan; Hellmich, Julia; Héroux, Annie; Ibrahim, Mohamed; Kern, Jan; Kuczewski, Anthony; Lemke, Henrik T; Liu, Pinghua; Majlof, Lars; McClintock, William M; Myers, Stuart; Nelsen, Silke; Olechno, Joe; Orville, Allen M; Sauter, Nicholas K; Soares, Alexei S; Soltis, S Michael; Song, Heng; Stearns, Richard G; Tran, Rosalie; Tsai, Yingssu; Uervirojnangkoorn, Monarin; Wilmot, Carrie M; Yachandra, Vittal; Yano, Junko; Yukl, Erik T; Zhu, Diling; Zouni, Athina

2016-04-05

X-ray free-electron lasers (XFELs) provide very intense X-ray pulses suitable for macromolecular crystallography. Each X-ray pulse typically lasts for tens of femtoseconds and the interval between pulses is many orders of magnitude longer. Here we describe two novel acoustic injection systems that use focused sound waves to eject picoliter to nanoliter crystal-containing droplets out of microplates and into the X-ray pulse from which diffraction data are collected. The on-demand droplet delivery is synchronized to the XFEL pulse scheme, resulting in X-ray pulses intersecting up to 88% of the droplets. We tested several types of samples in a range of crystallization conditions, wherein the overall crystal hit ratio (e.g., fraction of images with observable diffraction patterns) is a function of the microcrystal slurry concentration. We report crystal structures from lysozyme, thermolysin, and stachydrine demethylase (Stc2). Additional samples were screened to demonstrate that these methods can be applied to rare samples. Copyright © 2016 Elsevier Ltd. All rights reserved.

Dynamic Properties of DNA-Programmable Nanoparticle Crystallization.

PubMed

Yu, Qiuyan; Zhang, Xuena; Hu, Yi; Zhang, Zhihao; Wang, Rong

2016-08-23

The dynamics of DNA hybridization is very important in DNA-programmable nanoparticle crystallization. Here, coarse-grained molecular dynamics is utilized to explore the structural and dynamic properties of DNA hybridizations for a self-complementary DNA-directed nanoparticle self-assembly system. The hexagonal close-packed (HCP) and close-packed face-centered cubic (FCC) ordered structures are identified for the systems of different grafted DNA chains per nanoparticle, which are in good agreement with the experimental results. Most importantly, the dynamic crystallization processes of DNA hybridizations are elucidated by virtue of the mean square displacement, the percentage of hybridizations, and the lifetime of DNA bonds. The lifetime can be modeled by the DNA dehybridization, which has an exponential form. The lifetime of DNA bonds closely depends on the temperature. A suitable temperature for the DNA-nanoparticle crystallization is obtained in the work. Moreover, a too large volume fraction hinders the self-assembly process due to steric effects. This work provides some essential information for future design of nanomaterials.