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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1971-1979 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is possible to prepare “model” elastomeric networks having known values of the molecular weight Mc between crosslinks by endlinking functionally terminated polymer chains having number-average molecular weights Mn equal to the desired values of Mc. If chains having chemically inert groups at both ends are intentionally included during the preparation of such a system, they will remain unattached, merely reptating through the subsequently formed network structure. This technique was used to prepare a series of tetrafunctional polydimethylsiloxane (PDMS) networks having essentially the same degree of crosslinking (10-3Mc = 11.3 g mol-1) and constant amount of diluent in the form of unattached PDMS chains having molecular weights of 10-3Md = 26.4, 18.6, 15.8, 9.8, 6.7, 1.2, and 0.70 g mol-1. Because of the very high mobility of PDMS, it was also possible to introduce essentially the same amount of the same diluents into already formed PDMS networks having the same Mc. Extractions carried out using tetrahydrofuran at room temperature showed that the diluent (“sol fraction”) introduced by swelling the network is more easily removed than that present during the endlinking, possibly because of less convoluted arrangements within the network structure. Chains with the largest values of Md which were present during the endlinking were found to be very difficult to remove entirely. It is therefore extremely important to carry out exhaustive extractions to obtain reliable values of network sol fractions, particularly when such data are to be used to estimate extents of reaction in the preparation of end-linked elastomers.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Bimodal networks consisting of very short and relatively long poiydimethylsiloxane (PDMS) chains were studied from 30 to -52°C in an attempt to elucidate the anomalous increases in modulus [f*] exhibited by such elastomeric materials at high elongations. Temperature was found to have very little effect on (i) the elongation at which the upturn in [f*] becomes discernible, (ii) the elongation at which rupture occurs, and (iii) the total increase in [f*] up to the rupture point. The standard force-temperature (“thermoelastic”) plots were linear, but gave values of the energetic contribution to the total force which were significantly smaller than those universally obtained on unimodal, long-chain PDMS networks. Birefringence-temperature relations were also found to be linear, and yielded values of the optical-configuration parameter and its temperature coefficient which were in satisfactory agreement with the corresponding values reported for unimodal PDMS networks. These results indicate that even at very low temperatures the observed increases in modulus (and consequent improvements in ultimate strength) are due to non-Gaussian effects arising from limited chain extensibility, rather than from intermolecular reinforcing effects such as strain-induced crystallization.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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