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Keywords:

  • constraints;
  • dynamics;
  • elastomers;
  • entanglements;
  • Polymers;
  • reptation;
  • rubber modulus

Abstract

Polymer entanglements lead to complicated topological constraints and interactions between neighboring chains in a dense solution or melt. Entanglements can be treated in a mean field approach, within the famous reptation model, since they effectively confine each individual chain in a tube-like geometry. In polymer networks, due to crosslinks preventing the global reptation and constraint release, entanglements acquire a different topological meaning and have a much stronger effect on the resulting mechanical response. In this article we discuss two different models of rubber elasticity, both utilizing the reptation ideas. First, we apply the classical ideas of reptation statistics to calculate the effective rubber-elastic free energy of an entangled rubbery network. In the second approach, we examine the classical Rouse dynamics of chains with quenched constraints at their ends by crosslinks, and along the primitive path by entanglements. We then proceed to average a microscopic stress tensor for the network system and present it in a manageable form in the equilibrium t [RIGHTWARDS ARROW] ∞ limit. Particular attention is paid to the treatment of compressibility and hydrostatic pressure in a sample with open boundaries. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2679–2697, 2006