Effects of Concentration and Thermodynamic Interaction on the Viscoelastic Properties of Polymer Solutions

Ralph H. Colby, Lewis J. Fetters, Walter G. Funk, William W. Graessley

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Abstract

We report linear viscoelastic measurements for solutions of a high molecular weight polybutadiene covering the entire range of concentration from pure polymer to pure solvent at 25 °C. Two solvents were employed that have glass transition temperatures near that of polybutadiene: dioctyl phthalate is nearly a θ solvent at 25 °C and phenyloctane is a good solvent. We find three regimes of concentration for the viscosity in each solvent. In dilute solution (∅<4∅*) the viscosities are well represented by the Huggins equation, although with quite different intrinsic viscosities and Huggins coefficients in the two solvents. In the entangled semidilute range (∅c<∅< 0.1) and the concentrated regime (∅> 0.1) the free volume adjusted viscosity is identical in the two solvents and obeys power laws of ∅4 7 in semidilute solution and ∅3.6 in concentrated solution. Elastic response is also identical for the two solvents, with G°n (inferred from G″m) ∝1/J°e ∝ ∅2,3 for ∅ > 0.02. The results in semidilute solution compare favorably with the predictions of a recent two-parameter scaling theory. The observations also suggest that the concentration dependences of the characteristic molecular weights Me and Mc are somewhat different.

Original languageEnglish (US)
Pages (from-to)3873-3882
Number of pages10
JournalMacromolecules
Volume24
Issue number13
DOIs
StatePublished - Jun 1 1991

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All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

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