Characterization of entanglements in glassy polymeric ensembles using the Gaussian linking number

R Ahmad and S Paul and S Basu, PHYSICAL REVIEW E, 101, 022503 (2020).

DOI: 10.1103/PhysRevE.101.022503

We propose a method for enumerating entanglements between long chained, linear polymers that is based on the Gaussian linking number. The linking number is calculated between closely approaching segments of the macromolecular chains. Topological features of an entanglement, i.e., the extent to which one open segment winds around another, are reflected by the linking number. We show that using this measure, we can track disentanglement events through a deformation history and gain insights into how large scale disentanglements lead to failure. Incorporating an additional step where the topological entanglements identified along each chain are optimally clustered using standard clustering algorithms, we can also obtain a measure of the average number of rheological constraints that exist along each chain in an ensemble. Comparisons with other methods of enumerating entanglements, especially the primitive path analysis, are also made. Our results indicate that the linking number between two entangled segments in the undeformed state is a good indicator of the strength of the entanglement. Also, disentanglements occurring overwhelmingly around chain ends are an important cause of failure when a triaxial stress state exists in the polymer.

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