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Tuning polymer melt fragility with antiplasticizer additives

J. Chem. Phys. 126, 234903 (2007); doi:10.1063/1.2742382

Published 19 June 2007

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Robert A. Riggleman
Department of Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706

Jack F. Douglas
Polymers Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899

Juan J. de Pablo
Department of Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706
A polymer-diluent model exhibiting antiplasticization has been developed and characterized by molecular dynamics simulations. Antiplasticizer molecules are shown to decrease the glass transition temperature Tg but to increase the elastic moduli of the polymeric material in the low-temperature glass state. Moreover, the addition of antiplasticizing particles renders the polymer melt a stronger glass-forming material as determined by changes in the characteristic temperatures of glass formation, the fragility parameter D from fits to the Vogel-Folcher-Tamman-Hesse equation, and through the observation of the temperature dependence of the size of cooperatively rearranging regions (strings) in each system. The length of the strings exhibits a weaker temperature dependence in the antiplasticized glass-forming system than in the more fragile pure polymer, consistent with the Adam-Gibbs model of glass formation. Unexpectedly, the strings become increasingly concentrated in the antiplasticizer particles upon cooling. Finally, we discuss several structural indicators of cooperative dynamics, and find that the dynamic propensity (local Debye-Waller factor <u2>p) does seem to provide a strong correlation with local molecular displacements at long times. The authors also consider maps of the propensity, and find that the antiplasticized system exhibits larger fluctuations over smaller length scales compared to the pure polymer. ©2007 American Institute of Physics
History: Received 23 January 2007; accepted 27 April 2007; published 19 June 2007
Permalink: http://link.aip.org/link/?JCPSA6/126/234903/1
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KEYWORDS and PACS

Keywords
PACS
  • 61.20.Ja
    Computer simulation of liquid structure
  • 61.25.Hq
    Structure of macromolecular and polymer solutions, and polymer melts; swelling
  • 64.70.Pf
    Glass transitions
  • 62.20.Dc
    Elasticity, elastic constants
  • 81.40.Jj
    Elasticity and anelasticity, stress-strain relations
  • YEAR: 2007

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PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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