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  • Polymer and Materials Science  (3)
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  • 1
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermally stimulated depolarization currents (TSDC) technique has been used to study molecular motions around the glass transition in three different samples of poly(vinyl chloride) (PVC) varying in the contents of isotactic triads. The α-relaxation mode associated with cooperative molecular motions taking part in glass transition appears to be strongly dependent on tacticity. A secondary relaxation mode α′, different from the β-relaxation, has been detected just below the α-relaxation and at temperatures depending on the content of isotactic triads. Above the glass transition temperature the TSDC curves show a ρ-peak corresponding to the motion of free charges in the material. This process does not seem to be affected by tacticity. The results suggest that specific conformations of isotactic triads play an important role in the motion of chain segments in the polymer.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It has been shown that certain structural (X-ray diffraction) and physical (infrared dichroïsm, α-relaxation dynamics) characteristics of poly(vinyl chloride) undergo irreversible changes upon sample drawing. This behaviour reveals some non-equilibrium character of the polymer, even in tetrahydrofuran (THF) solution or in the rubbery state (at, typically, glass transition temperature Tg + 10°C). Two tentative ways of explanation have been proposed. The first one would attribute the cause of this peculiar behaviour to physical crosslinks linked to strong interchain bonding. These bonds would resist to dissolution in THF at room temperature but would be broken during stretching. The second way of explanation involves the presence of a metastable GTTG-TT conformation at the end of an isotactic sequence in an mmr chain segment. Like the above mentioned physical crosslinks, it would be transformed upon mechanical loading but not during dissolution in THF or heating to 90°C. Both hypotheses are not necessarily incompatible: as a matter of fact, GTTG- conformations at the end of the isotactic triads could represent sites of especially high intermolecular interaction, distributed along the polymeric chain.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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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
    Notes: Molecular motions of poly(vinyl chloride) (PVC) in the glass transition range were studied by means of dielectric spectroscopy. The measurements were carried out with three different PVC samples obtained at different polymerization temperatures (0, 60 and 90°C) showing strong variations in their contents of syndiotactic, heterotactic and isotactic triads. The results show that all parameters (relaxation strength, temperature of the maxima of loss curves, evolution of the shift factors, master curves) characterizing the dielectric α-relaxation in the liquid state of PVC are strongly affected by the tacticity. These facts are interpreted in terms of the role of specific local conformations in the motion of chain segments in the polymer molecules. These conclusions are in agreement with those outlined from the results previously obtained on PVC for the molecular motions in the glassy state just below the glass transition temperature.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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