Predictive relation for the α-relaxation time of a coarse-grained polymer melt under steady shear.

Giuntoli, Andrea; Puosi, Francesco; Leporini, Dino; Starr, Francis W; Douglas, Jack F · Sci Adv · 2020

basic_science · Level V

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Abstract

We examine the influence of steady shear on structural relaxation in a simulated coarse-grained unentangled polymer melt over a wide range of temperature and shear rates. Shear is found to progressively suppress the α-relaxation process observed in the intermediate scattering function, leading ultimately to a purely inertially dominated β-relaxation at high shear rates, a trend similar to increasing temperature. On the basis of a scaling argument emphasizing dynamic heterogeneity in cooled liquids and its alteration under material deformation, we deduce and validate a parameter-free scaling relation for both the structural relaxation time τ<sub>α</sub> from the intermediate scattering function and the "stretching exponent" β quantifying the extent of dynamic heterogeneity over the entire range of temperatures and shear rates that we can simulate.