Time-dependent orientation coupling in equilibrium polymer melts

The motion in concentrated polymer systems is described by either the Rouse or the reptation model, which both assume that the relaxation of each polymer chain is independent of the surrounding chains. This, however, is in contradiction with several experiments. In this Letter, we propose a universal description of orientation coupling in polymer melts in terms of the time-dependent coupling parameter κ(t). We use molecular dynamics simulations to show that the coupling parameter increases with time, reaching about 50% at long times, independently of the chain length or blend composition. This leads to predictions of component dynamics in mixtures of different molecular weights from the knowledge of monodisperse dynamics for unentangled melts. Finally, we demonstrate that entanglements do not play a significant role in the observed coupling. © 2010 The American Physical Societ

Determining tube theory parameters by slip-spring model simulations of entangled star polymers in fixed networks

Dynamical properties of branched polymer melts are determined by the polymer molecular weights and architectures containing junction points. Relaxation of entangled symmetric star polymers proceeds via arm-retraction and constraint release (CR). In this work, we investigate arm-retraction dynamics in the framework of a single-chain slip-spring model without CR effect where entanglements are treated as binary contacts, conveniently modeled as virtual ``slip-links'', each involving two neighboring strands. The model systems are analogous to isolated star polymers confined in a permanent network or a melt of very long linear polymers. We find that the distributions of the effective primitive path lengths are Gaussian, from which the entanglement molecular weight $N_e$, a key tube theory parameter, can be extracted. The procured $N_e$ value is in good agreement with that obtained from mapping the middle monomer mean-square displacements of entangled linear chains in slip-spring model to the tube model prediction. Furthermore, the mean first-passage (FP) times of destruction of original tube segments by the retracting arm end are collected in simulations and examined quantitatively using a theory recently developed in our group for describing FP problems of one-dimensional Rouse chains with improbable extensions. The asymptotic values of $N_e$ as obtained from the static (primitive path length) and dynamical (FP time) analysis are consistent with each other. Additionally, we manage to determine the tube survival function of star arms $\mu(t)$, or equivalently arm end-to-end vector relaxation function $\phi(t)$, through the mean FP time spectrum $\tau(s)$ of the tube segments after careful consideration of the inner-most entanglements

Shear banding in molecular dynamics of polymer melts

In order to establish constitutive equations for a viscoelastic fluid uniform shear flow is usually required. However, in the last 10 years S. Q. Wang and co-workers have demonstrated that some entangled polymers do not flow with the uniform shear rate as usually assumed, but instead choose to separate into fast and slow flowing regions. This phenomenon, known as shear banding, causes flow instabilities and in principle invalidates all rheological measurements when it occurs. In this Letter we report the first observation of shear banding in molecular dynamics simulations of entangled polymer melts. We show that our observations are in a very good agreement with the phenomenology developed by Fielding and Olmsted. Our findings provide a simple way of validating the empirical macroscopic phenomenology of shear banding. © 2012 American Physical Societ

Dynamic contact angle at nano-scale: a unified view

Generation of dynamic contact angle in the course of wetting is a fundamental phenomenon of nature. Dynamic wetting processes have a direct impact on flows at nano-scale, and therefore their understanding is exceptionally important to emerging technologies. Here, we reveal the microscopic mechanism of dynamic contact angle generation. It has been demonstrated using large-scale molecular dynamics simulations of bead-spring model fluids that the main cause of local contact angle variations is the distribution of microscopic force acting at the contact line region. We were able to retrieve this elusive force with high accuracy. It has been directly established that the force distribution can be solely predicted on the basis of a general friction law for liquid flow at solid surfaces by Thompson and Troian. The relationship with the friction law provides both an explanation of the phenomenon of dynamic contact angle and a methodology for future predictions. The mechanism is intrinsically microscopic, universal and irreducible, and is applicable to a wide range of problems associated with wetting phenomena

Arm retraction dynamics of entangled star polymers: a forward-flux sampling method study

The study of dynamics and rheology of well-entangled branched polymers remains a challenge for computer simulations due to the exponentially growing terminal relaxation times of these polymers with increasing molecular weights. We present an efficient simulation algorithm for studying the arm retraction dynamics of entangled star polymers by combining the coarse-grained slip-spring (SS) model with the forward-flux sampling (FFS) method. This algorithm is first applied to simulate symmetric star polymers in the absence of constraint release (CR). The reaction coordinate for the FFS method is determined by finding good agreement of the simulation results on the terminal relaxation times of mildly entangled stars with those obtained from direct shooting SS model simulations with the relative difference between them less than $5\%$. The FFS simulations are then carried out for strongly entangled stars with arm lengths up to $16$ entanglements that are far beyond the accessibility of brute force simulations in the non-CR condition. Apart from the terminal relaxation times, the same method can also be applied to generate the relaxation spectra of all entanglements along the arms which are desired for the development of quantitative theories of entangled branched polymers. Furthermore, we propose a numerical route to construct the experimentally measurable relaxation correlation functions by effectively linking the data stored at each interface during the FFS runs. The obtained star arm end-to-end vector relaxation functions $\Phi(t)$ and the stress relaxation function $G(t)$ are found to be in reasonably good agreement with standard SS simulation results in the terminal regime. Finally, we demonstrate that this simulation method can be conveniently extended to study arm-retraction problem in entangled star polymer melts with CR by modifying the definition of the reaction coordinate

Determination of tube theory parameters using a simple grid model as an example

Although the tube theory is successful in describing entangled polymers qualitatively, a more quantitative description requires precise and consistent definitions of its parameters. Here we investigate the simplest model of entangled polymers, namely a single Rouse chain in a cubic lattice of line obstacles, and illustrate the typical problems and uncertainties of the tube theory. In particular we show that in general one needs 3 entanglement related parameters, but only 2 combinations of them are relevant for the long-time dynamics. Conversely, the plateau modulus can not be determined from these two parameters and requires a more detailed model of entanglements with explicit entanglement forces, such as the slipsprings model. It is shown that for the grid model the Rouse time within the tube is larger than the Rouse time of the free chain, in contrast to what the standard tube theory assumes

Small angle neutron scattering observation of chain retraction after a large step deformation

The process of retraction in entangled linear chains after a fast nonlinear stretch was detected from time-resolved but quenched small angle neutron scattering (SANS) experiments on long, well-entangled polyisoprene chains. The statically obtained SANS data cover the relevant time regime for retraction, and they provide a direct, microscopic verification of this nonlinear process as predicted by the tube model. Clear, quantitative agreement is found with recent theories of contour length fluctuations and convective constraint release, using parameters obtained mainly from linear rheology. The theory captures the full range of scattering vectors once the crossover to fluctuations on length scales below the tube diameter is accounted for