1,374 research outputs found

    Investigating the void structure of the polyamide active layers of thin-film composite membranes

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    The potential presence of voids in the fully-aromatic polyamide active layers of thin-film composite (TFC) membranes for water purification was studied in a selection of commercial membranes with a broad range of performance levels. The membranes were characterized for their potential void fractions using three independent methods: (i) analysis of transmission electron microscopy (TEM) images of membrane cross-sections, (ii) water uptake measurements by quartz crystal microbalance (QCM), and (iii) estimates of the effective refractive indices of active layers by spectroscopic ellipsometry. Results revealed that voids having tens of nanometers in diameter exist in the fully-aromatic polyamide active layers of TFC membranes, the voids fill up with water when immersed in it, and the voids account for a significant volume fraction of the active layers (i.e., 15-32% for the membranes studied). It was concluded that the voids in polyamide active layers do not form passageways connecting the feed and permeate sides, but rather are cavities disconnected from the feed side. In addition, it was also concluded that the globular features observable in TEM images of membrane cross sections that had been previously identified as voids or nodules are indeed voids, and not nodules. The finding that a significant volume fraction of fully-aromatic polyamide active layers corresponds to water-filled voids has deep implications on various aspects of TFC membrane science and technology. For example, we illustrate how the presence of voids can potentially increase the effective water permeability of the active layer by as much as a factor of ≈5 compared with the case of an equivalent active layer without any voids. The methods developed in this study to measure void volume fraction represent useful tools for future membrane characterization studies, and the void fractions measured can be used as input or calibration parameters in future modeling studies of active layer formation or water and solute transport

    Spectroscopic Observations of Convective Patterns in the Atmospheres of Metal-Poor Stars

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    Convective line asymmetries in the optical spectrum of two metal-poor stars, Gmb1830 and HD140283, are compared to those observed for solar metallicity stars. The line bisectors of the most metal-poor star, the subgiant HD140283, show a significantly larger velocity span that the expectations for a solar-metallicity star of the same spectral type and luminosity class. The enhanced line asymmetries are interpreted as the signature of the lower metal content, and therefore opacity, in the convective photospheric patterns. These findings point out the importance of three-dimensional convective velocity fields in the interpretation of the observed line asymmetries in metal-poor stars, and in particular, urge for caution when deriving isotopic ratios from observed line shapes and shifts using one-dimensional model atmospheres. The mean line bisector of the photospheric atomic lines is compared with those measured for the strong Mg I b1 and b2 features. The upper part of the bisectors are similar, and assuming they overlap, the bottom end of the stronger lines, which are formed higher in the atmosphere, goes much further to the red. This is in agreement with the expected decreasing of the convective blue-shifts in upper atmospheric layers, and compatible with the high velocity redshifts observed in the chromosphere, transition region, and corona of late-type stars.Comment: 27 pages, LaTeX; 10 Figures (14 PostScript files); to be published in The Astrophysical Journa

    Answer Set Programming for Non-Stationary Markov Decision Processes

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    Non-stationary domains, where unforeseen changes happen, present a challenge for agents to find an optimal policy for a sequential decision making problem. This work investigates a solution to this problem that combines Markov Decision Processes (MDP) and Reinforcement Learning (RL) with Answer Set Programming (ASP) in a method we call ASP(RL). In this method, Answer Set Programming is used to find the possible trajectories of an MDP, from where Reinforcement Learning is applied to learn the optimal policy of the problem. Results show that ASP(RL) is capable of efficiently finding the optimal solution of an MDP representing non-stationary domains

    Oxygen abundances in unevolved metal-poor stars from near-UV OH lines

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    We have performed a detailed oxygen abundance analysis of 23 metal-poor (-3.0<[Fe/H]<-0.3) unevolved halo stars and one giant through the OH bands in the near UV, using high-resolution echelle spectra. Oxygen is found to be overabundant with respect to iron in these stars, with the [O/Fe] ratio increasing from 0.6 to 1 between [Fe/H]=-1.5 and -3.0. The behavior of the oxygen overabundance with respect to [Fe/H] is similar to that seen in previous works based on OI IR triplet data (Abia and Rebolo 1989; Tomkin et al. 1992; Cavallo, Pilachowski, and Rebolo 1997). Contrary to the previously accepted picture, our oxygen abundances, derived from low-excitation OH lines, agree well with those derived from high-excitation lines of the triplet. For nine stars in common with Tomkin et al. we obtain a mean difference of 0.00+/-0.11 dex with respect to the abundances determined from the triplet using the same stellar parameters and model photospheres. For four stars in our sample we have found measurements of the [OI] 6300 A line in the literature, from which we derive oxygen abundances consistent (average difference 0.09 dex) with those based on OH lines, showing that the long standing controversy between oxygen abundances from forbidden and permitted lines in metal-poor unevolved stars can be resolved. Our new oxygen abundances show a smooth extension of the Edvardsson et al.'s (1993) [O/Fe] versus metallicity curve to much lower abundances, with a slope -0.31+/- 0.11 (taking into account the error bars in both oxygen abundances and metallicities) in the range -3<[Fe/H]<-1.Comment: 17 pages, 8 figures, 3 table

    A Study of the Near-Ultraviolet Spectrum of Vega

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    UV, optical, and near-IR spectra of Vega have been combined to test our understanding of stellar atmospheric opacities, and to examine the possibility of constraining chemical abundances from low-resolution UV fluxes. We have carried out a detailed analysis assuming Local Thermodynamic Equilibrium (LTE) to identify the most important contributors to the UV continuous opacity: H, H^{-}, C I, and Si II. Our analysis also assumes that Vega is spherically symmetric and its atmosphere is well described with the plane parallel approximation. Comparing observations and computed fluxes we have been able to discriminate between two different flux scales that have been proposed, the IUE-INES and the HST scales, favoring the latter. The effective temperature and angular diameter derived from the analysis of observed optical and near-UV spectra are in very good agreement with previous determinations based on different techniques. The silicon abundance is poorly constrained by the UV observations of the continuum and strong lines, but the situation is more favorable for carbon and the abundances inferred from the UV continuum and optical absorption lines are in good agreement. Some spectral intervals in the UV spectrum of Vega that the calculations do not reproduce well are likely affected by deviations from LTE, but we conclude that our understanding of UV atmospheric opacities is fairly complete for early A-type stars.Comment: 13 pages, 9 figures, to be published in Ap

    On the Mechanism of the Copper-Catalyzed Enantioselective 1,4-Addition of Grignard Reagents to α,β-Unsaturated Carbonyl Compounds

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    The mechanism of the enantioselective 1,4-addition of Grignard reagents to α,β-unsaturated carbonyl compounds promoted by copper complexes of chiral ferrocenyl diphosphines is explored through kinetic, spectroscopic, and electrochemical analysis. On the basis of these studies, a structure of the active catalyst is proposed. The roles of the solvent, copper halide, and the Grignard reagent have been examined. Kinetic studies support a reductive elimination as the rate-limiting step in which the chiral catalyst, the substrate, and the Grignard reagent are involved. The thermodynamic activation parameters were determined from the temperature dependence of the reaction rate. The putative active species and the catalytic cycle of the reaction are discussed.
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