Composite entanglement topology and extensional rheology of symmetric ringlinear polymer blends
Abstract
Extensive molecular simulations are applied to characterize the equilibrium dynamics, entanglement topology, and nonlinear extensional rheology of symmetric ringlinear polymer blends with systematically varied ring fraction $\phi_R$. Chains with degree of entanglement $Z\approx14$ mixed to produce 10 wellentangled systems with $\phi_R$ varying from neat linear to neat ring melts. Primitive path analysis are used to visualize and quantify the structure of the composite ringlinear entanglement network. We directly measure the quantity of ringlinear threading and linearlinear entanglement as a function of $\phi_R$, and identify with simple arguments a ring fraction $\phi_R\approx0.4$ where the topological constraints of the entanglement network are maximized. These topological analyses are used to rationalize the $\phi_R$dependence of ring and linear chain dynamics, conformations, and blend viscosity. Complimentary simulations of startup uniaxial elongation flows demonstrate the extensional stress overshoot observed in recent filament stretching experiments, and characterize how it depends on the blend composition and entanglement topology. The overshoot is driven by an overstretching and recoil of ring polymer conformations that is caused by the convective unthreading of rings from linear chains. This produces significant changes in the entanglement structure of blends that we directly visualize and quantify with primitive path analyses during flow.
 Publication:

Journal of Rheology
 Pub Date:
 January 2022
 DOI:
 10.1122/8.0000319
 arXiv:
 arXiv:2107.01491
 Bibcode:
 2022JRheo..66...49O
 Keywords:

 Condensed Matter  Soft Condensed Matter;
 Condensed Matter  Materials Science
 EPrint:
 doi:10.1122/8.0000319