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Onset of entanglement and reptation in melts of linear homopolymers: consistent rheological simulations of experiments from oligomers to high polymers

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Abstract

The shear rheological behavior is investigated in this work for a series of poly(ethyl acrylate) samples, whose molar mass ranges from oligomers to high polymers. The focus was on studying the onset of entanglement effects over selected reptation models in order to ascertain their ability to reproduce the complex shear modulus of the polymers and to provide consistent values of the microscopic parameters driving the structural relaxation of the polymer system. Among ordinary reptation topological models, we found that the Doi–Edward model, implemented with contour length fluctuation and constraint release mechanism for the tube relaxation, better reproduced the rheological response of the materials. Most importantly, we were able to simulate material functions to obtain consistent microscopic information on the materials, such as Rouse time and entanglement molar mass, over the whole range of investigated molar masses, therefore overcoming the discrepancy usually found, mostly in the mass region of partial entanglement. Finally, descriptions of the polymer entanglement features, in agreement with the experimental and microscopic model findings, are provided in the framework of the packing-length phenomenological model and by means of analytical calculations of the polymer viscosity according to the Milner–McLeish–Likhtman model.

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Notes

  1. 1 In this paper, we follow the “G” convention for the definitions of entanglement spacing and time constants in the tube model treated extensively in Larson et al. (2003).

  2. 2 In van Ruymbeke et al. (2002), the number of free fitting parameters was 3 as well, but M e was a fixed parameter, while K d , K R , and M d were left free.

  3. 3 According to the approximations about CR presented in Likhtman and McLeish (2002), it is possible to calculate the viscosity analytically. In such a way, the calculation of η(M) depends on K R , K d , M/ M e , and c v . It is worth noting that for Z>10 calculations become insensitive to K R .

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Acknowledgments

The authors thank Prof. Valter Castelvetro for the synthesis of the samples.

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Authors and Affiliations

  1. Department of Physics “E. Fermi”, University of Pisa, Largo B. Pontecorvo 3, 56127, Pisa, Italy

    Fabio Zulli, Marco Giordano & Laura Andreozzi

  2. UOS di Pisa, IPCF-CNR, Via G. Moruzzi 1, 56124, Pisa, Italy

    Fabio Zulli, Marco Giordano & Laura Andreozzi

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  1. Fabio Zulli
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  2. Marco Giordano
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  3. Laura Andreozzi
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Correspondence to Laura Andreozzi.

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Zulli, F., Giordano, M. & Andreozzi, L. Onset of entanglement and reptation in melts of linear homopolymers: consistent rheological simulations of experiments from oligomers to high polymers. Rheol Acta 54, 185–205 (2015). https://doi.org/10.1007/s00397-014-0827-6

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  • DOI: https://doi.org/10.1007/s00397-014-0827-6

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