ABSTRACT
We present Monte Carlo computer simulations for melts of semiflexible randomly knotted and randomly concatenated ring polymers on the fcc lattice and in slit confinement. Through systematic variation of the slit width at fixed melt density, we explore the influence of confinement on single-chain conformations and interchain interactions. We demonstrate that confinement makes chains globally larger and more elongated while enhancing both contacts and knottedness propensities. As for multichain properties, we show that ring-ring contacts decrease with the confinement, yet neighboring rings overlap more as confinement grows. These aspects are accompanied by a marked decrease in the links formed between pairs of neighboring rings. In connection with the quantitative relation between links and entanglements in polymer melts recently established by us [Ubertini M. A.; Rosa A.Macromolecules2023, 56, 3354-3362], we propose that confinement can be used to set polymer networks that act softer under mechanical stress and suggest a viable experimental setup to validate our results.
ABSTRACT
The viscous flow of polymer chains in dense melts is dominated by topological constraints whenever the single-chain contour length, N, becomes larger than the characteristic scale Ne, defining comprehensively the macroscopic rheological properties of the highly entangled polymer systems. Even though they are naturally connected to the presence of hard constraints like knots and links within the polymer chains, the difficulty of integrating the rigorous language of mathematical topology with the physics of polymer melts has limited somehow a genuine topological approach to the problem of classifying these constraints and to how they are related to the rheological entanglements. In this work, we tackle this problem by studying the occurrence of knots and links in lattice melts of randomly knotted and randomly concatenated ring polymers with various bending stiffness values. Specifically, by introducing an algorithm that shrinks the chains to their minimal shapes that do not violate topological constraints and by analyzing those in terms of suitable topological invariants, we provide a detailed characterization of the topological properties at the intrachain level (knots) and of links between pairs and triplets of distinct chains. Then, by employing the Z1 algorithm on the minimal conformations to extract the entanglement length Ne, we show that the ratio N/Ne, the number of entanglements per chain, can be remarkably well reconstructed in terms of only two-chain links.
ABSTRACT
Current theories on the conformation and dynamics of unknotted and non-concatenated ring polymers in melt conditions describe each ring as a tree-like double-folded object. While evidence from simulations supports this picture on a single ring level, other works show pairs of rings also thread each other, a feature overlooked in the tree theories. Here we reconcile this dichotomy using Monte Carlo simulations of the ring melts with different bending rigidities. We find that rings are double-folded (more strongly for stiffer rings) on and above the entanglement length scale, while the threadings are localized on smaller scales. The different theories disagree on the details of the tree structure, i.e., the fractal dimension of the backbone of the tree. In the stiffer melts we find an indication of a self-avoiding scaling of the backbone, while more flexible chains do not exhibit such a regime. Moreover, the theories commonly neglect threadings and assign different importance to the impact of the progressive constraint release (tube dilation) on single ring relaxation due to the motion of other rings. Despite that each threading creates only a small opening in the double-folded structure, the threading loops can be numerous and their length can exceed substantially the entanglement scale. We link the threading constraints to the divergence of the relaxation time of a ring, if the tube dilation is hindered by pinning a fraction of other rings in space. Current theories do not predict such divergence and predict faster than measured diffusion of rings, pointing at the relevance of the threading constraints in unpinned systems as well. Revision of the theories with explicit threading constraints might elucidate the validity of the conjectured existence of topological glass.
ABSTRACT
We present computer simulations of a dynamic Monte Carlo algorithm for polymer chains on a fcc lattice which explicitly takes into account the possibility to overcome topological constraints by controlling the rate at which nearby polymer strands may cross through each other. By applying the method to systems of interacting ring polymers at melt conditions, we characterize their structure and dynamics by measuring, in particular, the amounts of knots and links which are formed during the relaxation process. In comparison with standard melts of unknotted and unconcatenated rings, our simulations demonstrate that the mechanism of strand crossing makes polymer dynamics faster provided the characteristic timescale of the process is smaller than the typical timescale for chain relaxation in the unperturbed state, in agreement with recent experiments employing solutions of DNA rings in the presence of the type II topoisomerase enzyme. In the opposite case of slow rates the melt is shown to become slower, and this prediction may be easily validated experimentally.
