Swelling and Residual Bond Orientations of Polymer Model Gels: The Entanglement-Free Limit

ORAL

Abstract





We investigate the swelling of polymer model networks prepared at different polymer volume fractions and in solvents of different quality. We extend the existing theory to describe residual bond orientations (the vector and the tensor order parameters) for theta, good, and athermal solvents and put these relations in context with modulus at preparation conditions and the equilibrium degree of swelling. We find good agreement with the assumption of affine swelling for the weakly entangled networks of our study. The same scaling relations (up to numerical coefficients) are obtained for the vector order parameter, m, and the tensor order parameter, S, as a function of the preparation conditions, network structure, the equilibrium degree of swelling, Q, and the modulus at swelling equilibrium, G. We obtain mQ–2 and Gm3/2 for swelling in theta solvents and mQ–1.08 with Gm2.14 in the good-solvent regime, in both cases independent of preparation conditions. Modulus and residual bond orientation are related by G ∝ φ0m and G ∝ φ01.23m as a function of the preparation polymer volume fraction φ0 for theta solvents and good solvents, respectively. Computer simulations and experimental data for the good-solvent regime show good agreement with the predictions.




*DFG grants no 397384169, 423478088, 423435302, 423373052, 423435431

Publication: Macromolecules 2022, 55, 14, 5997–6014.

Presenters

  • Michael Lang

    • Leibniz-Insitut für Polymerforschung

Authors

  • Michael Lang

    • Leibniz-Insitut für Polymerforschung
  • Reinhard Scholz

    • Leibniz Institut of Polymer Research, Hohe Straße 6, 01069 Dresden
  • Lucas Löser

    • Martin-Luther Universität Halle-Wittenberg, Institute of Physics - NMR Group, Betty-Heimann-Straße 7, D-06120 Halle/Saale, Germany
  • Carolin Bunk

    • Leibniz-Institut für Polymerforschung Dresden e.V., D-01069 Dresden
    • Leibniz-Institut für Polymerforschung Dresden e.V, D-01069 Dresden
    • Leibniz Institut für Polymerforschung, Hohe Straße 6, 01069 Dresden, Germany. Organic Chemistry of Polymers, Technische Universität Dresden, 01062 Dresden, Germany
  • Nora Fribiczer

    • Department of Chemistry, Johannes Gutenberg University Mainz, D-55128 Mainz
    • Johannes Gutenberg University Mainz, Department of Chemistry, Duesbergweg 10-14, D-55128 Mainz, Germany
  • Sebastian Seiffert

    • Department of Chemistry, Johannes Gutenberg University Mainz, D-55128 Mainz
    • Johannes Gutenberg University Mainz, Department of Chemistry, Duesbergweg 10-14, D-55128 Mainz, Germany
  • Frank Böhme

    • Leibniz-Institut für Polymerforschung Dresden e.V., D-01069 Dresden
    • Leibniz Institut für Polymerforschung, Hohe Straße 6, 01069 Dresden, Germany
  • Kay Saalwaechter

    • University of Halle-Wittenberg