Evidence that self-similar microrheology of highly entangled polymeric solutions scales robustly with, and is tunable by, polymer concentration

TL;DR

This study demonstrates that the microrheology of highly entangled polymer solutions exhibits a robust, self-similar scaling with concentration, which can be tuned by polymer concentration and molecular weight, revealing predictable power-law behaviors.

Contribution

It provides evidence that the self-similar microrheology scales with concentration across different polymer types and molecular weights, extending previous findings to synthetic solutions.

Findings

MSD follows a power-law form within a specific lag time range.

The MSD exponent varies linearly with concentration.

The MSD pre-factor varies exponentially with concentration.

Abstract

We report observations of a remarkable scaling behavior with respect to concentration in the passive microbead rheology of two highly entangled polymeric solutions, polyethylene oxide (PEO) and hyaluronic acid (HA). This behavior was reported previously [Hill et al., PLOS ONE (2014)] for human lung mucus, a complex biological hydrogel, motivating the current study for synthetic polymeric solutions PEO and HA. The strategy is to identify, and focus within, a wide range of lag times ${\tau}$ for which passive micron diameter beads exhibit self-similar (fractional, power law) mean-squared-displacement (MSD) statistics. For lung mucus, PEO at three different molecular weights (Mw), and HA at one Mw, we find ensemble-averaged MSDs of the form ${\langle}{\Delta}r^{2}({\tau}){\rangle} = 4D_{\alpha}{\tau}^{\alpha}$, all within a common band, [1/60 sec, 3 sec], of lag times ${\tau}$. We employ the MSD power law parameters $(D_{\alpha},{\alpha})$ to classify each polymeric solution over a range of highly entangled concentrations. By the generalized Stokes-Einstein relation, power law MSD implies power law elastic $G'({\omega})$ and viscous $G''({\omega})$ moduli for frequencies $1/{\tau}$, [0.33 sec$^{-1}$, 60 sec$^{-1}$]. A natural question surrounds the polymeric properties that dictate $D_{\alpha}$ and ${\alpha}$, e.g. polymer concentration c, Mw, and stiffness (persistence length). In [Hill et al., PLOS ONE (2014)], we showed the MSD exponent ${\alpha}$ varies linearly, while the pre-factor $D_{\alpha}$ varies exponentially, with concentration, i.e. the semi-log plot, $(log(D_{\alpha}),{\alpha})(c)$ of the classifier data is collinear. Here we show the same result for three distinct Mw PEO and HA at a single Mw. Future studies are required to explore the generality of these results for polymeric solutions, and to understand this scaling behavior with polymer concentration.