Rheology of Ring Polymer Melts: From Linear Contaminants to Ring/Linear Blends

Abstract

Ring polymers remain a major challenge to our current understanding of polymer dynamics. Experimental results are difficult to interpret because of the uncertainty in the purity and dispersity of the sample. Using both equilibrium and non-equilibrium molecular dynamics simulations we have systematically investigated the structure, dynamics and rheology of perfectly controlled ring/linear polymer blends with chains of such length and flexibility that the number of entanglements is up to about 14 per chain, which is comparable to experimental systems examined in the literature. The smallest concentration at which linear contaminants increase the zero-shear viscosity of a ring polymer melt of these chain lengths by 10% is approximately one-fifth of their overlap concentration. When the two architectures are present in equal amounts the viscosity of the blend is approximately twice as large as that of the pure linear melt. At this concentration the diffusion coefficient of the rings is found to decrease dramatically, while the static and dynamic properties of the linear polymers are mostly unaffected. Our results are supported by a primitive path analysis.

5 pages, 4 figures, accepted by PRL

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• Topological analysis of polymeric melts: Chain length effects and fast-converging estimators for entanglement length
• Molecular Dynamics Simulation Study of Nonconcatenated Ring Polymers in a Melt: II. Dynamics
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