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  • 1
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 14 (1954), S. 193-208 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: For the description of the practical properties of a large number of linear polymer molecules as well as for the discussion of the various mean parameters of the individual chain molecule, the model usually employed to represent the molecule consists of N m straight line chain elements of length A m statistically joined to each other (straight element model). For the construction of large-scale wire models of polymer molecules to be used in model experiments on the hydrodynamic behavior of chain molecules, a somewhat different model (circular segment model) was employed in previous papers. In these papers the relationships connecting the parameters which characterize these two models respectively have been determined on the basis of certain assumptions. These assumptions, as has recently been shown, were however partly in error and certain corrections have now to be applied to the numerical constants which appear in previously published formulas for the diffusion and sedimentation constants and for the intrinsic viscosity and streaming birefringence. The formulas, resulting after these corrections have been incorporated, are compiled in the present paper and the effect of these corrections on the interpretation of both new and old experimental results is discussed. It is found that agreement between theory and experiment is improved by the use of the corrected expressions and that in particular certain discrepancies which had previously existed between the lengths A m of the statistical chain element as calculated from sedimentation and diffusion experiments, on the one hand, and viscosity determinations on the other, disappear after these corrections are applied (see Table I).
    Additional Material: 3 Ill.
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  • 2
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Tab.
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  • 3
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Filaments of polyvinyl alcohol crosslinked by dry heating reach a swelling equilibrium without dissolving in water or in a N/10 acetate buffer solution. The addition of Cu••-ions to the swollen filaments produces an additional crosslinking, associated with an increased E-modulus and a contraction of the filament. Comparison shows that the efficiency per crosslink with respect to the E-modulus increase is about 6 to 8 times smaller in the case of Cu••-crosslinking of swollen polyvinyl alcohol than in the case of non swollen rubber crosslinking. This difference is attributed to the use of a great part of the reagent in case of polyvinyl alcohol for producing network portions with an exceptionally low network filament molecular weight, leaving the high length of other filament parts practically unchanged. In the case of an inhomogeneous filament weight distribution a small value of the E-modulus efficiency factor fE per crosslink can be expected.
    Notes: Fäden aus Polyvinylalkohol wurden zunächst im homogenen Zustande thermisch vernetzt, so daß sie in Wasser bzw. in einem n/10 Na-Acetatpuffer stark quellen, ohne sich zu lösen. Die gequollenen Folien wurden anschließend durch Einwirkung von Cu••-Ionen zusätzlich vernetzt. Es tritt dabei eine Kontraktion der Folien sowie eine Erhöhung des E-Moduls ein. Die durch Einwirkung eines Cu••-Ions herbeigeführte Erhöhung des E-Moduls wird verglichen mit der beispielsweise bei Kautschuk durch die Bildung eines Vernetzungspunktes herbeigeführten E-Modul-Erhöhung, gemessen am homogenen und am anschließend an die Vernetzung gequollenen Kautschuk.Die Wirksamkeit je Vernetzungspunkt ist bei der Cu••-Vernetzung des gequollenen Polyvinylalkohols etwa 6 bis 8 mal kleiner als die Wirksamkeit je Vernetzungspunkt beim homogenen Kautschuk. Das Auftreten eines E-Modul-Wirksamkeitsfaktors fE von der Größe 1/6 bis 1/8 bei der Cu••-Vernetzung des gequollenen Polyvinylalkohols wird in erster Linie dadurch gedeutet, daß beim hoch gequollenen Polyvinylalkoholgel ein großer Teil des Vernetzungsreagenses für die Bildung von Netzwerkteilen mit sehr kleinem Netzbogengewicht verwendet wird. Es entsteht dann an Stelle eines homogenen ein hinsichtlich der Netzbogengewichtsverteilung stark unhomogenes Netzwerk, für welches ein stark unterhalb 1 liegender E-Modul-Wirksamkeitsfaktor modellmäßig zu erwarten ist.
    Additional Material: 2 Ill.
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  • 4
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The YOUNG's modulus E′ and the POISSON number μ′ of a swollen gel sample, stretched in an embedding fluid of constant activity, are different from the YOUNG's modulus E and the POISSON number μ of the same gel sample stretched at constant mass of the swelling agent in the sample. A relation between the four elastic constants derived recently was confirmed by experiment.
    Notes: Zwei verschiedene Bedingungen, unter denen eine gequollene Folie elastisch verformt werden kann, sind: 1. Dehnung bei konstanter Zusammensetzung, insbesondere bei konstantem Gehalt des Gelfadens an Quellungsmittel und 2. Streckung bei konstantem Partialdruck des Quellungsmittels. Die Elastizitätsmodule E, E′ und die POISSONschen Zahlen μ, μ′ für diese beiden Dehnungsbedingungen werden definiert und experimentell festgestellt. Eine quantitative beziehung zwischen diesen vier Größen, die in einer früheren Arbeit hergeleitet worden war, konnte experimentell bestätigt werden.
    Additional Material: 2 Ill.
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