4.7 Article

The relaxation dynamics of single flow-stretched polymers in semidilute to concentrated solutions

Journal

JOURNAL OF CHEMICAL PHYSICS
Volume 154, Issue 2, Pages -

Publisher

AIP Publishing
DOI: 10.1063/5.0037513

Keywords

-

Ask authors/readers for more resources

This paper investigates the time evolution of the linear dimensions of a single finitely extensible Rouse polymer in a solution of other polymers under linear mixed flow using a generalized Langevin equation (GLE). The decay of the chain's fractional extension in the steady state is shown to be expressed in terms of a linear combination of Mittag-Leffler and generalized Mittag-Leffler functions, suggesting a non-exponential melt relaxation process with a continuous spectrum of timescales. The calculated decay curves provide satisfactory fits to experimental data, indicating the potential role of the tube model's two-step mechanism in chain relaxation processes.
Recent experiments on the return to equilibrium of solutions of entangled polymers stretched by extensional flows [Zhou and Schroeder, Phys. Rev. Lett. 120, 267801 (2018)] have highlighted the possible role of the tube model's two-step mechanism in the process of chain relaxation. In this paper, motivated by these findings, we use a generalized Langevin equation (GLE) to study the time evolution, under linear mixed flow, of the linear dimensions of a single finitely extensible Rouse polymer in a solution of other polymers. Approximating the memory function of the GLE, which contains the details of the interactions of the Rouse polymer with its surroundings, by a power law defined by two parameters, we show that the decay of the chain's fractional extension in the steady state can be expressed in terms of a linear combination of Mittag-Leffler and generalized Mittag-Leffler functions. For the special cases of elongational flow and steady shear flow, and after adjustment of the parameters in the memory function, our calculated decay curves provide satisfactory fits to the experimental decay curves from the work of Zhou and Schroeder and earlier work of Teixeira et al. [Macromolecules 40, 2461 (2007)]. The non-exponential character of the Mittag-Leffler functions and the consequent absence of characteristic decay constants suggest that melt relaxation may proceed by a sequence of steps with an essentially continuous, rather than discrete, spectrum of timescales.

Authors

I am an author on this paper
Click your name to claim this paper and add it to your profile.

Reviews

Primary Rating

4.7
Not enough ratings

Secondary Ratings

Novelty
-
Significance
-
Scientific rigor
-
Rate this paper

Recommended

No Data Available
No Data Available