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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1897-1915 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The isothermal adsorption of high-and low-molecular-weight poly(γ-benzyl-L-glutamate) (PBLG) onto (100) alkali-halide surfaces has been studied with the intent of developing a model for the adsorption process. Data from both the solution and adsorbed phases were correlated in this study. The α-helical conformation was maintained in solution and on the substrate for all molecular weights investigated. Fourier-transform infrared spectroscopy proved to be a sensitive technique for conformational analysis of adsorbed PBLG films as thin as 200 Å. High-molecular-weight PBLG was adsorbed as an interwoven fibrous mat, homogeneously covering the entire substrate surface. This morphology was independent of the substrate. Adsorption of low-molecular-weight PBLG took on a lamellar morphology, often exhibiting epitaxial orientation in the substrate 〈100〉 directions. Quasielastic laser light scattering studies showed that low-molecular-weight PBLG had a much higher degree of aggregation in nonpolar solvents than did high-molecular-weight PBLG. The proposed adsorption model is essentially a modification of one suggested by Silberberg. It involves segmental adsorption of aggregates, as opposed to single macromolecules of PBLG. The unadsorbed segments of the aggregates form a concentrated interfacial region directly above the substrate. Further interaction and association of PBLG may occur in this region, thus reducing the epitaxial ordering influence of the substrate. Consequently, polymers which do not interact strongly in the concentrated interfacial region, such as polyethylene, are expected to be adsorbed epitaxially, as has been reported.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 787-798 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The epitactic behavior of a single chain of polyoxymethylene and of polythiomethylene on alkali halide substrates has been simulated by computing the coulombic, induced dipolar, and dispersion-repulsive potential energies as a function of polymer-substrate geometry. Inspection of the total potential energy surface for a polyoxymethylene chain in a 9/5 helix reveals a favorable alignment in which the chain is parallel to the substrate surface ((001) cleavage plane) with specific positioning along rows of positive charge. This preferential orientation has been found to be independent of lattice matching between the substrate and deposited phase. An identical mode of orientation is predicted for a polyoxymethylene chain and a polythiomethylene chain, both in the 2/1 cis-planar conformation. The theoretical results for polyoxymethylene are in agreement with available experimental evidence, whereas the outcomes of the calculations performed on polythiomethylene should be considered predictive study to be complemented by a future experimental investigation.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1813-1825 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An initial series of energy calculations is aimed at predicting the epitactic behavior of S2N2 as deposited from the vapor phase upon NaCl-type alkali halide substrates and preferred orientation of molecular chains in the (SN)x polymerized phase. Although the preferred orientation of a single S2N2 molecule is identical for NaCl and NaF, the energetics of dimer formation on the surface greatly favor use of the latter substrate as a heterogeneous nucleation catalyst. Enhancement of dimer formation on NaF is due to a near match between S2N2-S2N2 equilibrium distance and substrate unit-cell spacing. Furthermore, the (SN)x chain-orientation tendency also appears to be a function of alkali halide type. On NaCl, the chain axis lies along the 〈110〉 surface direction above cationic rows, the plane of interatomic bonds being perpendicular to the surface. For NaF the axial direction is 〈100〉 with alignment between rows of alternating charge, with the molecular plane in this case parallel to the substrate surface. From the calculations it appears that primary Coulombic forces are not a significant factor in dictating the epitactic properties of monomer or polymer.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 2185-2197 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of energy calculations have been carried out in order to describe the epitaxial crystallization of polyethylene from solution in terms of molecular interactions. The total energy has been computed as the sum of electrostatic, dispersion, and repulsion contributions. The potential energy associated with a section of a planar-zigzag polyethylene chain has been determined for various orientations and positions above three different planar alkali halide substrates. Inspection of the energy surfaces as a function of the spatial degrees of freedom reveals that the minimum energy orientation of the chain is that for which it is parallel to the substrate [(001) cleavage plane] and aligned in the 〈110〉 direction on the surface, a result in accordance with available experimental evidence. Specifically, the chain preference is to position itself along rows of positive ions, whereas alignment along rows of negative charge appears energetically unfavorable. The mode of chain orientation is virtually independent of lattice matching criteria. Dispersionrepulsive forces have been found to be most sensitive to orientation and greater in magnitude than the electrostatic forces.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 311-320 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A number of theoretical approaches to the problem of free volume in polymers are discussed. Because some questions in the Bueche approach remain unresolved, the lattice-gas model was studied. Inconsistencies in the independent-vacancy approximation led to consideration of a mean-field model and then a precise Padé-approximant solution, neither of which gave satisfactory agreement with experiment. Introduction of an internal pressure parameter to model the effects of the chainlike structure of polymers restores agreement with experiment.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 399-409 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymer-substrate interaction energetics have been determined in order to describe the epitaxial deposition of polyethylene into graphite. The potential energy was calculated using van der Waal's interactions. A closed-form representation of the potential was derived for a substrate which was considered infinite in planar area. Inspection of the relative polymer-substrate energies for various positions above the substrate indicate a planar-zigzag polyethylene chain segment deposits with its backbone parallel to the substrate. The chain axis preferentially orients in the (1120) directions of the graphite surface layer. Specifically, deposition occurs along the lines which intersect the nearest-neighbor midpoints of the C—C bonds in the surface layer.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 2017-2026 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Molecular mechanics energy calculations have been used to assess the relative affinities that an iodobenzene solvent molecule and a segment of a polyoxymethylene chain have for five different alkali halide (001) surfaces. Dispersive-repulsive and coulombic contributions to the interaction energy have been included. The calculated interaction deposition energy correlates well with the nucleation density of rodlike epitaxial crystals formed on these substrates in epitaxial crystallization experiments from solution. Substrates which have a higher preference for solvent (LiF and NaF) than for polymer exhibit relatively low polymer nucleation densities. As the degree of solvent preference decreases, and polymer preference increases, higher nucleation densities are observed (KCI and KI). These results suggest that preferential solvent adsorption may account for the low nucleation densities observed on some substrates in polymer epitaxial crystallization experiments from solution.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 2003-2016 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Epitaxial crystallization of polyoxymethylene (POM) from 0.5% iodobenzene solution has been attempted between 150 and 165°C on 11 different substrates having surface energies ranging from 136 to 1240 ergs/cm2. Included in this series are several substrates such as CaF2, SrF2, BaF2, graphite, mica, and silicon which had not been previously tested as substrates for POM epitaxy. The fluorite series materials are not good substrates for the epitaxial crystallization of POM from solution. In contrast, both rodlike and fold-plane epitaxial morphologies have been found on the (001) surfaces of NaCl, NaF, and mica. A possible mechanism for the formation of fold-plane epitaxy is discussed which involves solution nucleation followed by adsorption and growth of the nuclei on the substrate. It is suggested that variations observed in nucleation density of rodlike epitaxial crystals from substrate to substrate are a result of differences in degree of preferential solvent adsorption. Substrates having higher surface energies should tend to adsorb solvent more strongly and thus inhibit profuse nucleation of polymer crystals on the surface.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2933-2940 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: For a series of menthol esters of increasing size and polarity, “mintyness” decreased rapidly as molecular weight increased. For molecular weights above about 700, the compounds were tasteless to a significant proportion of the taste panel. As polarity increased, the “sweet minty” taste of hydrophobic menthol esters became increasingly bitter, until water-soluble menthol esters were strongly bitter. Bitterness was still apparent in quite high-molecular-weight water-soluble esters; a different receptor may be involved for bitterness than for mint. An overall hypothesis relating flavor to molecular solubility parameters is proposed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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