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Experimental study on the capillary thinning of entangled polymer solutions

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Abstract

The transient elongation behavior of entangled polymer and wormlike micelles (WLM) solutions has been investigated using capillary breakup extensional rheometry (CaBER). The transient force ratio X = 0.713 reveals the existence of an intermediate Newtonian thinning region for polystyrene and WLM solutions prior to the viscoelastic thinning. The exponential decay of X(t) in the first period of thinning defines an elongational relaxation time λ x which is equal to elongational relaxation time λ e obtained from exponential diameter decay D(t) indicating that the initial stress decay is controlled by the same molecular relaxation process as the strain hardening observed in the terminal regime of filament thinning. Deviations in true and apparent elongational viscosity are discussed in terms of X(t). A minimum Trouton ratio is observed which decreases exponentially with increasing polymer concentration leveling off at Trmin = 3 for the solutions exhibiting intermediate Newtonian thinning and Trmin ≈ 10 otherwise. The relaxation time ratio λ e/ λ s, where λ s is the terminal shear relaxation time, decreases exponentially with increasing polymer concentration and the data for all investigated solutions collapse onto a master curve irrespective of polymer molecular weight or solvent viscosity when plotted versus the reduced concentration c[ η], with [ η] being the intrinsic viscosity. This confirms the strong effect of the nonlinear deformation in CaBER experiments on entangled polymer solutions as suggested earlier. On the other hand, λ e ≈λ s is found for all WLM solutions clearly indicating that these nonlinear deformations do not affect the capillary thinning process of these living polymer systems.

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Acknowledgments

The authors would like to thank Sonja Müller, Sebastian Bindgen, and Frank Bossler for their help in sample preparation and performing the experiments.We would like to thank Jonathan Rothstein and Sunil Khandavalli (University of Massachusetts) for the possibility to use the FiSER setup and for all help given. Financial support by German Research Foundation DFG grant WI 3138/13-1 is gratefully acknowledged.

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  1. Institute for Mechanical Process Engineering and Mechanics, Group Applied Mechanics (AME), Karlsruhe Institute of Technology (KIT), Gotthard-Franz-Straße 3, 76131, Karlsruhe, Germany

    Dirk Sachsenheimer, Bernhard Hochstein & Norbert Willenbacher

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  1. Dirk Sachsenheimer
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Sachsenheimer, D., Hochstein, B. & Willenbacher, N. Experimental study on the capillary thinning of entangled polymer solutions. Rheol Acta 53, 725–739 (2014). https://doi.org/10.1007/s00397-014-0789-8

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