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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Journal of inorganic and organometallic polymers and materials 1 (1991), S. 505-530 
    ISSN: 1572-8870
    Keywords: Thermochromism ; fluorescence ; polysilanes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermochromic behavior of a number of dialkyl-substituted polysilanes has been studied in some detail. The formation of a long wavelength-absorbing species in solution at low temperatures is dependent on the polymer structure. Evidence for polymer aggregation has been found in solutions as dilute as 10−5 M (based on the monomer unit). Fluorescence emission studies at very low concentrations (〈10−6 M) suggest that single-molecule events can result in the observed thermochromic changes. We have obtained no evidence for the proposed coil-to-rod transition at low temperature by either light or neutron scattering; indeed the scattering studies seem to suggest that the polymer coil dimensions actually shrink slightly prior to the onset of aggregation. It is proposed that the thermochromism observed for many dialkyl polysilanes in solution is initiated by the formation of extended segments within a polymer chain which are long enough to stabilize intra- and intersegmental interactions. In extremely dilute solutions this interaction results in a shrinkage of a single polymer chain; at higher concentrations the interaction results in aggregation.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 2335-2349 
    ISSN: 0887-6266
    Keywords: morphology ; polysilanes ; thin film ; chain orientation ; spectroscopy ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of confinement on the crystallinity and chain orientation of ultrathin poly(di-n-hexylsilane) films has been investigated using UV absorption, fluorescence and IR spectroscopies. UV absorption measurements in a series of poly(di-n-hexylsilane) films having thicknesses between 50 and 3500 Å have shown that, for thicknesses less than 500 Å, the polymer backbone disorders and extensive crystallization of the films is hindered irrespective of molecular weight or surface hydrophobicity. Fluorescence studies showed that rapid energy transfer occurs from the disordered chain segments to the crystalline ones. The orientation of both the polymer backbone and side chains was probed with IR absorption and grazing incidence reflection measurements. The side chains are extended, although not completely in the all-trans conformation, with their carbon plane mostly perpendicular to the substrate. The backbone lies extended, with the polymer axis parallel to the plane of the film. The hexyl side-chains disorder in films less than 2000 Å thick and this disordering occurs through the introduction of gauche bonds. Our findings suggest the possibility of using thickness to control the chain organization and morphology of a polymer thin film. © 1996 John Wiley & Sons, Inc.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
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