Viscoelasticity of randomly branched polymers in the vulcanization class

Charles P. Lusignan, Thomas H. Mourey, John C. Wilson, Ralph H. Colby

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We report viscosity, recoverable compliance, and molar mass distribution for a series of randomly branched polyester samples with long linear chain sections between branch points. Molecular structure characterization determines [Formula Presented] for the exponent controlling the molar mass distribution, so this system belongs to the vulcanization (mean-field) universality class. Consequently, branched polymers of similar size strongly overlap and form interchain entanglements. The viscosity diverges at the gel point with an exponent [Formula Presented] that is significantly larger than the value of 1.33 predicted by the branched polymer Rouse model (bead-spring model without entanglements). The recoverable compliance diverges at the percolation threshold with an exponent [Formula Presented] This effect is consistent with the idea that each branched polymer of size equal to the correlation length stores [Formula Presented] of elastic energy. Near the gel point, the complex shear modulus is a power law in frequency with an exponent [Formula Presented] The measured rheological exponents confirm that the dynamic scaling law [Formula Presented] holds for the vulcanization class. Since s is larger and u is smaller than the Rouse values observed in systems that belong to the critical percolation universality class, we conclude that entanglements profoundly increase the longest relaxation time. Examination of the literature data reveals clear trends for the exponents s and u as functions of the chain length between branch points. These dependencies, qualitatively explained by hierarchical relaxation models, imply that the dynamic scaling observed in systems that belong to the vulcanization class is nonuniversal.

Original languageEnglish (US)
Pages (from-to)5657-5669
Number of pages13
JournalPhysical Review E - Statistical Physics, Plasmas, Fluids, and Related Interdisciplinary Topics
Issue number5
StatePublished - Jan 1 1999

All Science Journal Classification (ASJC) codes

  • Statistical and Nonlinear Physics
  • Statistics and Probability
  • Condensed Matter Physics


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