A Topologically Driven Glass in Ring Polymers

Abstract

The static and dynamic properties of ring polymers in concentrated solutions remains one of the last deep unsolved questions in Polymer Physics. At the same time, the nature of the glass transition in polymeric systems is also not well understood. In this work we study a novel glass transition in systems made of circular polymers by exploiting the topological constraints that are conjectured to populate concentrated solutions of rings. We show that such rings strongly inter-penetrate through one another, generating an extensive network of topological interactions that dramatically affects their dynamics. We show that a kinetically arrested state can be induced by randomly pinning a small fraction of the rings. This occurs well above the classical glass transition temperature at which microscopic mobility is lost. Our work demonstrates both the existence of long-lived inter-ring penetrations and also realises a novel, topologically-induced, glass transition.

Accepted version; To appear in PNAS. 13 pages, main text+SI. Supplementary movies can be found at the URL: http://www2.ph.ed.ac.uk/~dmichiel/

References in corpus (9)

• Theoretical perspective on the glass transition and amorphous materials
• Glassy dynamics of kinetically constrained models
• Molecular Dynamics Simulation Study of Nonconcatenated Ring Polymers in a Melt: I. Statics
• Molecular Dynamics Simulation Study of Nonconcatenated Ring Polymers in a Melt: II. Dynamics
• Direct measurements of growing amorphous order and non-monotonic dynamic correlations in a colloidal glass-former
• Growing Dynamical Facilitation on Approaching the Random Pinning Colloidal Glass Transition
• Slowing down of ring polymer diffusion caused by inter-ring threading
• Understanding the dynamics of rings in the melt in terms of annealed tree model
• Non-linear dynamic response of glass-forming liquids to random pinning

Cited by in corpus (26)

• Glassiness and Heterogeneous Dynamics in Dense Solutions of Ring Polymers
• On the Tree-Like Structure of Rings in Dense Solutions
• Viscosity Overshoot in Biaxial Elongational Flow: Coarse-Grained Molecular Dynamics Simulation of Ring-Linear Polymer Mixtures
• Topological Linking Determines Elasticity in Limited Valence Networks
• Local loop opening in untangled ring polymer melts: A detailed "Feynman test" of models for the large scale structure
• Topological free volume and quasi-glassy dynamics in melt of ring polymers
• Entanglement length scale separates threading from branching of unknotted and non-concatenated ring polymers in melts
• Persistence Homology Of Entangled Rings
• Segment-Scale, Force-Level Theory of Mesoscopic Dynamic Localization and Entropic Elasticity in Entangled Chain Polymer Liquids
• Topological Kinetic Crossover in a Nanomagnet Array
• Fluidification of Entangled Polymers by Loop Extrusion
• A simple and general approach for reversible condensation polymerization with cyclization
• Geometric Learning of Knot Topology
• Effects of chain length on Rouse modes and non-Gaussianity in linear and ring polymer melts
• Brownian motion of flexibly-linked colloidal rings
• Polymer threadings and rigidity dictate the viscoelasticity and nonlinear relaxation dynamics of entangled ring-linear blends and their composites with rigid rod microtubules
• Unraveling the glass-like dynamic heterogeneity in ring polymer melts: From semi-flexible to stiff chain
• Marginally compact fractal trees with semiflexibility
• Marginally compact hyperbranched polymer trees
• Dynamical properties of different models of elastic polymer rings: confirming the link between deformation and fragility
• Reversible stepwise condensation polymerization with cyclization: strictly alternating co-polymerization and homopolymerization based upon two orthogonal reactions
• Glass formation in mechanically interlocked ring polymers: the role of induced chain stiffness
• Ring polymers in two-dimensional melts double-fold around randomly branching "primitive shapes"
• Hydrodynamic Inflation of Ring Polymers under Shear
• Topological digestion drives time-varying rheology of entangled DNA fluids
• Physical entanglements mediate coherent motion of the active topological glass confined within a spherical cavity