Temperature dependent micro-rheology of a glass-forming polymer melt studied by molecular dynamics simulation

Inspired by advances in the chemical synthesis of interlocking polymer architectures, extensive molecular dynamics simulations have been conducted to study the dynamical properties of poly[n]catenanes—polymers composed entirely of interlocking rings—in the melt state. Both the degree of polymerization (number of links) and the number of beads per ring are systematically varied, and the results are compared to linear and ring polymers. A simple Rouse-like model is presented, and its analytical solution suggests a decomposition of the dynamics into “ring-like” and “linear-like” regimes at short and long times, respectively. In agreement with this picture, multiple sub-diffusive regimes are observed in the monomer mean-squared-displacements even though interchain entanglement is not prevalent in the system. However, the Rouse-type model does not account for the topological effects of the mechanical bonds, which significantly alter the dynamics at intermediate length scales both within the rings and at the chain segment scales. The stress relaxation in the system is extremely rapid and may be conveniently separated into ring-like and linear-like contributions, again in agreement with the Rouse picture. However, the viscosity has a non-monotonic dependence on the ring size for long chains, which disagrees strongly with theoretical predictions. This unexpected observation cannot be explained in terms of chain disentanglement and is inconsistent with other measures of polymer relaxation. Possible mechanisms for this behavior are proposed and implications for materials design are discussed.

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Active one-particle microrheology of an unentangled polymer melt studied by molecular dynamics simulation

Kuhnhold

Paul

2015

Phys. Rev. E

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We present molecular dynamics simulations for active one-particle microrheology of an unentangled polymer melt. The tracer particle is forced to oscillate by an oscillating harmonic potential, which models an experiment using optical tweezers. The amplitude and phase shift of this oscillation are related to the complex shear modulus of the polymer melt. In the linear response regime at low frequencies, the active microrheology gives the same result as the passive microrheology, where the thermal motion of a tracer particle is related to the complex modulus. We expand the analysis to include full hydrodynamic effects instead of stationary Stokes friction only, and show that different approaches suggested in the literature lead to completely different results, and that none of them improves on the description using the stationary Stokes friction.

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Temperature dependent micro-rheology of a glass-forming polymer melt studied by molecular dynamics simulation

Cited by 4 publications

References 38 publications

Linear Viscoelasticity of Polymers and Polymer Nanocomposites: Molecular-Dynamics Large Amplitude Oscillatory Shear and Probe Rheology Simulations

Linear Viscoelasticity of Polymers and Polymer Nanocomposites: Molecular-Dynamics Large Amplitude Oscillatory Shear and Probe Rheology Simulations

Dynamics of poly[n]catenane melts

Active one-particle microrheology of an unentangled polymer melt studied by molecular dynamics simulation

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