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  • 1
    Publication Date: 2017-07-28
    Description: The water-gas shift (WGS) reaction (where carbon monoxide plus water yields dihydrogen and carbon dioxide) is an essential process for hydrogen generation and carbon monoxide removal in various energy-related chemical operations. This equilibrium-limited reaction is favored at a low working temperature. Potential application in fuel cells also requires a WGS catalyst to be highly active, stable, and energy-efficient and to match the working temperature of on-site hydrogen generation and consumption units. We synthesized layered gold (Au) clusters on a molybdenum carbide (α-MoC) substrate to create an interfacial catalyst system for the ultralow-temperature WGS reaction. Water was activated over α-MoC at 303 kelvin, whereas carbon monoxide adsorbed on adjacent Au sites was apt to react with surface hydroxyl groups formed from water splitting, leading to a high WGS activity at low temperatures.
    Keywords: Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 62 (1997), S. 213-221 
    ISSN: 0020-7608
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular orbital calculations of sixfold barriers in nitromethane, methyl boron difluoride, and trifluoronitromethane were performed by various Hartree-Fock and electron correlation methods. In those calculations, staggered and eclipsed conformations are of primary concern. These results indicated that for CH3NO2 and CH3BF2 the staggered conformations are more stable, while CF3NO2 has a more stable conformation in an eclipsed form. Both conformations do not differ significantly, which may account for the low internal rotational barrier of each molecule. Values of the barrier calculated by the Møller-Plesset perturbation and the quadratic configuration interaction methods did not match the experimental results. However, better internal rotational barrier values of each molecule were observed when the improved better basis sets and the Hartree-Fock method were selected. © 1997 John Wiley & Sons, Inc.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 53 (1994), S. 485-496 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A new route (“direct forming”) was developed for forming dense PBI shapes from PBI powder. The new process affords the possibility of automated PBI powder shaping (“cold compaction”) and densification in batches of multiple parts by a “powder-assisted hot isostatic pressing” process. Direct forming is a more productive alternative to hot compression molding. Two developments enable PBI direct forming: (1) the discovery that PBI powders that are porous and plasticized with moisture can be shaped by compaction at ambient temperatures (cold-compacted), and (2) a finding that cold-compacted shapes can be densified in large batches by a powder-assisted hot isostatic pressing. The porous PBI powder is formed from PBI in solution by a spray-precipitation process. When plasticized with moisture, this powder is cold-compactible to PBI shapes with densities up to 94% of that of ultimate density of PBI. These shapes, which have sufficient strength to be handled, are then further consolidated via powder-assisted hot isostatic pressing to shapes with excellent thermal and mechanical properties and densities of about 99% of the ultimate. © 1994 John Wiley & Sons, Inc.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The effects of fiber volume content, fiber-matrix bonding, heat treatment, and age hardening on the transverse mechanical properties of undirectional aluminum matrix fibrous composites have been investigated. Test results have indicated that the increase of the matrix strength is directly responsible for the increase of the transverse strength of a composite fabricated under heat-treated conditions, as compared with the corresponding strength for the annealed condition. The composite transverse tensile strength and elastic modulus have been calculated by using the finite-element method and the von Mises-Hencky criterion. Both the square and hexagonal arrays have been considered for the fiber configuration in the matrix. The analytical results are compared with the experimental data obtained at room temperature and low strain rate.
    Additional Material: 17 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 10 (1970), S. 43-47 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: In this paper the results of both the theoretical and experimental stress analyses of composite materials reinforced with ribbons are presented. The reinforcing materials for such composites are characterized as two-dimensional elements which are isotropic in planes parallel to the faces. The theoretical work is based on the finite element method. Experimentally, the photoelastic technique is employed to determine the stresses around the glass ribbons embedded in an epoxy matrix. The specimens, containing a number of aligned ribbons, were loaded in tension parallel to the ribbon width. The variation of shearing stress at the ribbon-matrix interface as well as the pertubation effect on both the ribbon normal stress and interfacial shear due to the discontinuity of the neighboring ribbons are discussed.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 11 (1971), S. 51-56 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The longitudinal strengths of unidirectional discontinuous fiber composites have been calculated based on the concept of perturbation effect and the distortional energy criterion, utilizing the finite-element method. The theoretical results thus obtained are compared with the experimental data as well as the results of shear lag analysis for tungsten-copper, boron-aluminum, glass-epoxy and boron-epoxy composites. Based on the Jackson-Cratchley equations, modified for discontinuous fibers, a formula is also proposed for calculating the strengths of randomly oriented discontinuous fiber composites. The results calculated from this formula are compared with the experimental data for aluminum oxide-aluminum-silicon and glass-epoxy composites.
    Additional Material: 8 Ill.
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  • 7
    ISSN: 0021-9304
    Keywords: bonding-strength ; shear-strength ; simulated body fluid ; push-out measurement ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine , Technology
    Notes: This study was undertaken to evaluate the effect of coating characteristics on the mechanical strengths of the plasma-sprayed HA-coated Ti-6Al-4V implant system both in vitro and in vivo. Two types of HA coatings (HACs) with quite different microstructures, concentrations of impurity-phases, and indices-of-crystallinity were used. In vitro testings were done by measuring the bonding-strength at the Ti-6Al-4V-HAC interface, with HACs that had and had not been immersed in a pH-buffered, serum-added simulated body fluid (SBF). The shear-strength at the HAC-bone interface was investigated in a canine transcortical femoral model after 12 and 24 weeks of implantation. The results showed a bonding degradation of approximately 32% or higher of the original strength after 4 weeks of immersion in SBF, and this predominantly depended on the constructed microstructure of the HACs. After the push-out measurements, it was demonstrated that the HACs with higher bonding-strength in vitro would correspondingly result in significantly higher shear-strength at each implant period in vivo. Nevertheless, there were no substantial histological variations between the two types of HACs evaluated. The most important point elucidated in this study was that, among coating characteristics, the microstructure was the key factor in influencing the mechanical stability of the HACs both in vitro and in vivo. As a consequence, a denser HAC was needed to ensure mechanical stability at both interfaces. © 1997 John Wiley & Sons, Inc. J Biomed Mater Res, 37, 335-345, 1997.
    Additional Material: 9 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    Surface and Interface Analysis 26 (1998), S. 984-994 
    ISSN: 0142-2421
    Keywords: ToF-SIMS ; SIMS ; metal ; contamination ; Si ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Volumetric relative sensitivity factors (RSFs) are determined for 52Cr, 56Fe and 58Ni in an O2+-formed silicon oxide using a 12 keV Ga+ primary ion beam, and the influence of matrix oxygen content on these RSF values is evaluated. A multivariate expression for Si2+-referenced RSF values as a function of oxygen content is developed. This expression indicates that 12 keV Ga+ ion beam RSF values for 52Cr, 56Fe and 58Ni in O2+-formed oxide at 1.0 nm depth are in excellent agreement with well-established 8 keV O2+ RSF values in a silicon matrix. Because calculated RSF values for O2+-formed oxide at 1.0 nm depth and native silicon oxide are almost equivalent, time-of-flight (ToF) SIMS metal RSF values and detection limits in native oxide for a Ga+ liquid metal ion source are predicted, using the well-established 8 keV O2+ RSF values for metals in a silicon matrix. Time-of-flight SIMS silicon surface detection limits of 5×106 to 5×108 atoms cm-2 @ 0.5 nm are predicted for most metals of interest to the semiconductor community. © 1998 John Wiley & Sons, Ltd.
    Additional Material: 9 Ill.
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  • 9
    Publication Date: 2016-09-02
    Description: Direct methods for stereoselective functionalization of sp 3 -hybridized carbon–hydrogen [C(sp 3 )–H] bonds in complex organic molecules could facilitate much more efficient preparation of therapeutics and agrochemicals. Here, we report a copper-catalyzed radical relay pathway for enantioselective conversion of benzylic C–H bonds into benzylic nitriles. Hydrogen-atom abstraction affords an achiral benzylic radical that undergoes asymmetric C(sp 3 )–CN bond formation upon reaction with a chiral copper catalyst. The reactions proceed efficiently at room temperature with the benzylic substrate as limiting reagent, exhibit broad substrate scope with high enantioselectivity (typically 90 to 99% enantiomeric excess), and afford products that are key precursors to important bioactive molecules. Mechanistic studies provide evidence for diffusible organic radicals and highlight the difference between these reactions and C–H oxidations mediated by enzymes and other catalysts that operate via radical rebound pathways.
    Keywords: Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 10
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2017-10-20
    Description: In chain-growth polymerization, a chain grows continually to reach thousands of subunits. However, the real-time dynamics of chain growth remains unknown. Using magnetic tweezers, we visualized real-time polymer growth at the single-polymer level. Focusing on ring-opening metathesis polymerization, we found that the extension of a growing polymer under a pulling force does not increase continuously but exhibits wait-and-jump steps. These steps are attributable to the formation and unraveling of conformational entanglements from newly incorporated monomers, whose key features can be recapitulated with molecular dynamics simulations. The configurations of these entanglements appear to play a key role in determining the polymerization rates and the dispersion among individual polymers.
    Keywords: Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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