Results from numerical simulations of polymers under shear flow are compared with predictions for shear banding based on a model coupling Rolie-Poly-like tube dynamics to the entanglement dynamics mediated by Convected Constraint Release (CCR). CCR is controlled by a parameter $β$, whose dependence on the bending stiffness $k_θ$ is calculated from the simulations. The model predicts shear banding for polymers whose equilibrium entanglement number $Z$ exceeds a critical value $Z_{c}$ that depends on $β$. The simulations are in semi-quantitative agreement with the model, with deviations that are attributed to approximations inherent in the model, and the inadequacy of tube models to describe partially-disentangled liquids in strong flow. These results may help determine which physical polymers could undergo shear banding.
Based on numerical modeling with the diffusive Giesekus constitutive equation, a recent Letter [Phys. Rev. Lett. 120, 138002 (2018), arXiv:1801.08798] claimed that the experimental reports of shear banding in entangled polymeric fluids were due to the disturbances from the sample edge. The conclusion that true bulk shear banding is precluded in the presence of edge effects is at odds with many past experimental, theoretical, numerical, and computer simulation studies. We briefly discuss some problems of this work.
We investigate theoretically shear banding in large amplitude oscillatory shear (LAOS) of polymers and wormlike micelles. In LAOStrain we find banding at low frequencies and sufficiently high strain rate amplitudes in fluids for which the underlying constitutive curve of shear stress as a function of shear rate is non-monotonic. This is the direct analogue of quasi steady state banding seen in slow strain rate sweeps along the flow curve. At higher frequencies and sufficiently high strain amplitudes we report a different but related phenomenon, which we call `elastic' shear banding. This is as…
In 1975 Doi and Edwards predicted that entangled polymer melts and solutions can have a constitutive instability, signified by a decreasing stress for shear rates greater than the inverse of the reptation time. Experiments did not support this, and more sophisticated theories incorporated Marrucci's idea (1996) of removing constraints by advection; this produced a monotonically increasing stress and thus stable constitutive behavior. Recent experiments have suggested that entangled polymer solutions may possess a constitutive instability after all, and have led some workers to question the val…
Edge instabilities are believed to be one of the possible causes of shear banding in entangled polymeric fluids. Here, we investigate the effect of edge disturbance on the shear-induced dynamics of well-entangled DNA solutions. Using a custom high-aspect-ratio planar-Couette cell, we systematically measure the velocity profiles of sheared DNA samples at different distances away from the edge of the shear cell. Under a weak oscillatory shear with the corresponding Weissenberg number (Wi) smaller than 1, where DNA solutions exhibit linear velocity profiles with strong wall slip, the penetration …
Using high-resolution confocal rheometry, we study the shear profiles of well-entangled DNA solutions under large amplitude oscillatory shear (LAOS) in a rectilinear planar shear cell. With increasing Weissenberg number (Wi), we observe successive transitions from normal Newtonian linear shear profiles to wall-slip dominant shear profiles and finally to shear-banding profiles at high Wi. To investigate the microscopic origin of the observed shear banding, we study the dynamics of micron-sized tracers embedded in DNA solutions. Surprisingly, tracer particles in the shear frame exhibit transient…
Amorphous solids are critical in the design and production of nanoscale devices, but under strong confinement these materials exhibit changes in their mechanical properties which are not well understood. Phenomenological models explain these properties by postulating an underlying defect structure in these materials but do not detail the microscopic properties of these defects. Using machine learning methods, we identify mesoscale defects that lead to shear banding in polymer nanopillars well below the glass transition temperature as a function of pillar diameter. Our results show that the pri…
Homogeneous polymer solutions are well-known to exhibit viscoelastic flow instabilities: purely elastic when inertia is negligible, inertio-elastic otherwise. Recently, shear-banding wormlike micelles solutions were also discovered to follow a similar phenomenology. In the shear-banding regime, inertia is usually negligible so only purely elastic flows have been reported. Here, we investigate a non-shear-banding solution where inertia becomes significant, leading to flow patterns akin to the inertio-elastic regime of dilute polymer solutions. We show that the instability follows a supercritica…
Wang [Phys. Rev. Lett. 103, 219801 (2009)] makes the following points about our Letter [Phys. Rev. Lett. 102, 067801 (2009), arXiv:0805.0679]: (1) He infers that, "contrary to its title, shear banding emerged from monotonic curves only if there was a stress gradient", and he points out that nonquiescent relaxation was found (experimentally) after step strain in geometries without a stress gradient. (2) He disagrees with the values of the parameters we used. (3) In some recent experiments the flow was homogeneous after cessation of step strain, and only subsequently developed nonquiescent macro…
We study theoretically the formation of shear bands in time-dependent flows of polymeric and wormlike micellar surfactant fluids, focussing on the protocols of step shear stress, step shear strain (or in practice a rapid strain ramp), and shear startup, which are commonly studied experimentally. For each protocol we perform a linear stability analysis to provide a fluid-universal criterion for the onset of shear banding, following our recent Letter [Phys. Rev. Lett. 110 (2013) 086001]. In each case this criterion depends only on the shape of the experimentally measured rheological response fun…
Despite decades of research, the question of whether solutions and melts of highly entangled polymers exhibit shear banding as their steady state response to a steadily imposed shear flow remains controversial. From a theoretical viewpoint, an important unanswered question is whether the underlying constitutive curve of shear stress $σ$ as a function of shear rate $\dotγ$ (for states of homogeneous shear) is monotonic, or has a region of negative slope, $dσ/d\dotγ<0$, which would trigger banding. Attempts to settle the question experimentally via velocimetry of the flow field inside the fluid …
In the shear flow of liquid crystalline polymers (LCPs) the nematic director orientation can align with the flow direction for some materials, but continuously tumble in others. The nematic dumbbell (ND) model was originally developed to describe the rheology of flow-aligning semi-flexible LCPs, and flow-aligning LCPs are the focus in this paper. In the shear flow of monodomain LCPs it is usually assumed that the spatial distribution of the velocity is uniform. This is in contrast to polymer solutions, where highly non-uniform spatial velocity profiles have been observed in experiments. We ana…
Spatially inhomogeneous shear flow occurs in entangled polymer solutions, both as steady state shear banding and transiently after a large step strain or during start up to a steady uniform shear rate. Steady state shear banding is a hallmark of models with a non-monotonic constitutive relation between total shear stress and applied shear rate, but transient banding is sometimes seen in fluids that do not shear band at steady state. We model this behavior using the diffusive Rolie-Poly model in a Newtonian solvent, whose constitutive behavior can be monotonic or non-monotonic depending on the …
We study the dynamics of the Taylor-Couette flow of shear banding wormlike micelles. We focus on the high shear rate branch of the flow curve and show that for sufficiently high Weissenberg numbers, this branch becomes unstable. This instability is strongly sub-critical and is associated with a shear stress jump. We find that this increase of the flow resistance is related to the nucleation of turbulence. The flow pattern shows similarities with the elastic turbulence, so far only observed for polymer solutions. The unstable character of this branch led us to propose a scenario that could acco…
We review the experimental and theoretical results obtained during the past decade on the structure and rheology of wormlike micellar solutions. We focus on the linear and nonlinear viscoelasticity and emphasize the analogies with polymers. Based on a comprehensive survey of surfactant systems, the present study shows the existence of standard rheological behaviors for semidilute and concentrated solutions. One feature of this behavior is a shear banding transition associated with a stress plateau in the nonlinear mechanical response. For concentrated solutions, we show that in the plateau reg…
Within a highly generalised theoretical framework for the flow properties of complex fluids, we study the onset of shear banding in the three most common time-dependent experimental protocols: step stress, step strain and shear startup. By means of a linear stability analysis we derive a fluid-universal criterion for the onset of banding, separately for each protocol, that depends only on the shape of the experimentally measured time-dependent rheological response function, independent of the constitutive law and internal state variables of the particular fluid in question. Our predictions thu…
The interplay between shear band (SB) formation and boundary conditions (BC) is investigated in wormlike micellar systems (CPyCl--NaSal) using ultrasonic velocimetry coupled to standard rheology in Couette geometry. Time-resolved velocity profiles are recorded during transient strain-controlled experiments in smooth and sand-blasted geometries. For stick BC standard SB is observed, although depending on the degree of micellar entanglement temporal fluctuations are reported in the highly sheared band. For slip BC wall slip occurs only for shear rates larger than the start of the stress plateau.…
To predict flow behavior of entangled polymer melt, we have developed multiscale simulation composed of Lagrangian fluid particle simulation and coarse-grained polymer dynamics simulation. We have introduced a particle deformation in the Lagrangian fluid particle simulation to describe elongation flow at a local point. The particle deformation is obtained to be consistent with the local polymer deformation.
A mode-coupling theory for dense polymeric systems is developed which unifyingly incorporates the segmental cage effect relevant for structural slowing down and polymer chain conformational degrees of freedom. An ideal glass transition of polymer melts is predicted which becomes molecular-weight independent for large molecules. The theory provides a microscopic justification for the use of the Rouse theory in polymer melts, and the results for Rouse-mode correlators and mean-squared displacements are in good agreement with computer simulation results.
Molecular dynamics simulation of a generic polymer model is applied to study melts of polymers with different types of intrinsic stiffness. Important static observables of the single chain such as gyration radius or persistence length are determined. Additionally we investigate the overall static melt structure including pair correlation function, structure function and orientational correlation function.
Polymer melts undergoing large deformation by uniaxial elongation are studied by molecular dynamics simulations of bead-spring chains in melts. Applying a primitive path analysis to strongly deformed polymer melts, the role of topological constrains in highly entangled polymer melts is investigated and quantified. We show that the over-all, large scale conformations of the primitive paths (PPs) of stretched chains follow affine deformation while the number and the distribution of entanglement points along the PPs do not. Right after deformation, PPs of chains retract in both directions paralle…
Equilibration of polymer melts containing highly entangled long polymer chains in confinement or with free surfaces is a challenge for computer simulations. We approach this problem by first studying polymer melts based on the soft-sphere coarse-grained model confined between two walls with periodic boundary conditions in two directions parallel to the walls. Then we apply backmapping to reinsert the microscopic details of the underlying bead-spring model. Tuning the strength of the wall potential, the monomer density of confined polymer melts in equilibrium is kept at the bulk density even ne…
We propose that several mechanisms contribute to friction in a polymer melt adsorbed at a structured surface. The first one is the well known disentanglement of bulk polymer chains from the surface layer. However, if the surface is ideal at the atomic scale, the adsorbed parts of polymer chains can move along the equipotential lines of the surface potential. This gives rise to a strong slippage of the melt. For high shear rates chains partially desorb. However, the friction force on adsorbed chains increases, resulting in quasi-stick boundary conditions. We propose that the adsorbed layers can…
The generalized entropy theory (GET) offers many insights into how molecular parameters influence polymer glass-formation. Given the fact that chain rigidity often plays a critical role in understanding the glass-formation of polymer materials, the GET was originally developed based on models of semiflexible chains. Consequently, all previous calculations within the GET considered polymers with some degree of chain rigidity. Motivated by unexpected results from computer simulations of fully flexible polymer melts concerning the dependence of thermodynamic and dynamic properties on the cohesive…
The calculation of discrete or continuous relaxation time spectra from rheometric measurables of polydisperse polymers is an ill-posed problem. In this paper, a curve fitting method for solving this problem is presented and compared to selected models from the literature. It is shown that the new method is capable of correctly predicting the molecular mass distributions of linear polydisperse polymer melts as well as their relaxation time spectra.
We have developed a new multiscale simulation technique to investigate history-dependent flow behavior of entangled polymer melt, using a smoothed particle hydrodynamics simulation with microscopic simulators that account for the dynamics of entangled polymers acting on each fluid element. The multiscale simulation technique is applied to entangled polymer melt flow around a circular obstacle in a two-dimensional periodic system. It is found that the strain-rate history-dependent stress of the entangled polymer melt affects its flow behavior, and the memory in the stress causes nonlinear behav…
We perform molecular dynamics simulations of an idealized polymer melt surrounding a nanoscopic filler particle to probe the effects of a filler on the local melt structure and dynamics. We show that the glass transition temperature $T_g$ of the melt can be shifted to either higher or lower temperatures by appropriately tuning the interactions between polymer and filler. A gradual change of the polymer dynamics approaching the filler surface causes the change in the glass transition. We also find that while the bulk structure of the polymers changes little, the polymers close to the surface te…
The radius of gyration of a polymer chain immersed in a low molecular weight solvent is known to vary monotonically with the solvent quality. Here, we consider the behavior of a chain immersed in a high molecular weight solvent (polymer melt). Unsurprisingly, we find that, as the incompatibility between the chain and the polymer melt is increased, the two limiting conformations of the chain are the ideal random coil (R = aN^1/2) and the dense globule (R = aN^1/3). We show, however, that between these two limits the radius of gyration of the chain presents a hysteretic behavior .
The lattice cluster theory (LCT) for semiflexible linear telechelic melts, developed in paper I, is applied to examine the influence of chain stiffness on the average degree of self-assembly and the basic thermodynamic properties of linear telechelic polymer melts. Our calculations imply that chain stiffness promotes self-assembly of linear telechelic polymer melts that assemble on cooling when either polymer volume fraction $ϕ$ or temperature $T$ is high, but opposes self-assembly when both $ϕ$ and $T$ are sufficiently low. This allows us to identify a boundary line in the $ϕ$-$T$ plane that …
Plateau moduli of Kremer-Grest models for commodity polymer melts
University of Southern Denmark（南丹麦大学）；ENSL, CNRS, Laboratoire de Physique (UMR 5672) and Centre Blaise Pascal de l’École Normale Supérieure de Lyon（里昂高等师范学院、法国国家科学研究中心物理实验室（UMR 5672）及里昂高等师范学院布莱兹·帕斯卡中心）
In polymer physics it is typically assumed that excluded volume interactions are effectively screened in polymer melts. Hence, chains could be described by an effective random walk without excluded volume interactions. In this letter, we show that this mapping is problematic by analyzing the occurrence of knots, their spectrum and sizes in polymer melts, corresponding random walks and chains in dilute solution. The effective random walk severely overrates the occurrence of knots and their complexity, particularly when compared to melts of flexible chains, indicating that non-trivial effects du…
We study structural properties of a ring polymeric melt confined in a film in comparison to a linear counterpart using molecular dynamics simulations. Local structure orderings of ring and linear polymers in the vicinity of the surface are similar to each other because the length scale of surface-monomer excluded volume interaction is smaller than the size of an ideal blob of the ring. In a long length scale, while the Silberberg hypothesis can be used to provide a physical origin of confined linear polymer results, it no longer holds for a ring polymer case. We also present different structur…
We perform molecular-dynamics simulations for polymer melts of the coarse-grained polyvinyl alcohol model that crystallizes upon slow cooling. To establish the properties of its high temperature liquid state as a reference point, we characterize in detail the structural features of equilibrated polymer melts with chain lengths $5\le N \le 1000$ at a temperature slightly above their crystallization temperature. We find that the conformations of sufficiently long polymers with $N >50$ obey essentially the Flory's ideality hypothesis. The chain length dependence of the end-to-end distance and the…
We have mapped the physics of polymer melts onto a time-dependent Landau-Ginzburg $|ψ|^4$ field theory using techniques of functional integration. Time in the theory is simply a label for the location of a given monomer along the extent of a flexible chain. With this model, one can show that the limit of infinitesimal concentration of a polymer melt corresponds to a {\em dynamic} critical phenomenon. The transition to the entangled state is also shown to be a critical point. For larger concentrations, when the role of fluctuations is reduced, a mean field approximation is justifiably employed …
The Kremer-Grest (KG) model is a standard for studying generic polymer properties. Here we have equilibrated KG melts up to and beyond $200$ entanglements per chain for varying chain stiffness. We present methods for estimating the Kuhn length corrected for incompressibility effects, for estimating the entanglement length corrected for chain stiffness, for estimating bead frictions and Kuhn times taking into account entanglement effects. These are the key parameters for enabling quantitative, accurate, and parameter free comparisons between theory, experiment and simulations of KG polymer mode…
We investigated the elongational flows of the weakly entangled linear polymer melt using a coarse-grained molecular dynamics simulation. We extended the uniform extensional flow (UEF) method developed by Nicholson and Rutledge (D. A. Nicholson and G. C. Rutledge, J. Chem. Phys., 145, 244903 (2016)) for application to Langevin dynamics. We succeeded in observing the elongational viscosity of the weakly entangled linear polymer melt from the equilibrium state to the steady state using the extended UEF method, whereas the conventional rectangular parallelepiped shape technique for extensional flo…
The lattice cluster theory (LCT) for the thermodynamics of polymer systems has recently been reformulated to treat strongly interacting self-assembling polymers composed of fully flexible linear telechelic chains [J. Dudowicz and K. F. Freed, J. Chem. Phys. \textbf{136}, 064902 (2012)]. Here, we further extend the LCT for linear telechelic polymer melts to include a description of chain semiflexibility, which is treated by introducing a bending energy penalty whenever a pair of consecutive bonds from a single chain lies along orthogonal directions. An analytical expression for the Helmholtz fr…
Kinetic barriers cause polymers to crystallize incompletely, into nanoscale lamellae interleaved with amorphous regions. As a result, crystalline polymers are full of crystal-melt interfaces, which dominate their physical properties. The longstanding theoretical challenge to understand these interfaces has new relevance, because of accumulating evidence that polymer crystals often nucleate via a metastable, partially ordered "rotator" phase. To test this idea requires a theory of the bulk and interfacial free energies of the critical nucleus. We present a new approach to the crystal-melt inter…
The slip behavior of polydimethylsiloxane (PDMS) polymer melts flowing on non-adsorbing surfaces made of short non-entangled PDMS chains densely end-grafted to silica has been characterized. For high enough shear rates, constant slip lengths proportional to the bulk fluid viscosity have been observed, in agreement with Navier's interfacial equation, and demonstrating that the interfacial Navier's friction coefficient is a local quantity, independent of the polymer molecular weight. Comparing the interfacial shear stresses deduced from these measured slip lengths to available friction stress me…
We investigate the impact of nanoparticles (NP) on the fragility and cooperative string-like motion in a model glass-forming polymer melt by molecular dynamics simulation. The NP cause significant changes to both the fragility and the average length of string-like motion, where the effect depends on the NP-polymer interaction and the NP concentration. We interpret these changes via the Adam-Gibbs (AG) theory, assuming the strings can be identified with the "cooperatively rearranging regions" of AG. Our findings indicate fragility is primarily a measure of the temperature dependence of the coop…
We propose a simple mean-field theory for the structure of ring polymer melts. By combining the notion of topological volume fraction and a classical van der Waals theory of fluids, we take into account many body effects of topological origin in dense systems. We predict that although the compact statistics with the Flory exponent $ν=1/3$ is realized for very long chains, most practical cases fall into the crossover regime with the apparent exponent $ν= 2/5$ during which the system evolves toward a topological dense-packed limit.
We investigate mutual local chain order in systems of fully flexible polymer melts in a simple generic bead-spring model. The excluded-volume interaction together with the connectivity leads to local ordering effects which are independent of chain length between 25 and 700 monomers, i.e. in the Rouse as well as in the reptation regime. These ordering phenomena extend to a distance of about 3 to 4 monomer sizes and decay to zero afterwards.
The Kremer-Grest (KG) polymer model is a standard model for studying generic polymer properties in Molecular Dynamics simulations. It owes its popularity to its simplicity and computational efficiency, rather than its ability to represent specific polymers species and conditions. Here we show, that by tuning the chain stiffness it is possible to adapt the KG model to model melts of real polymers. In particular, we provide mapping relations from KG to SI units for a wide range of commodity polymers. The connection between the experimental and the KG melts is made at the Kuhn scale, i.e. at the …
Recent experiments in some polymer melts quenched below the melting temperature have reported spinodal kinetics in small-angle X ray scattering before the emergence of crystalline structure. To explain these observations we propose that the coupling between density and chain conformation induces a liquid-liquid binodal within the equilibrium liquid--crystalline solid coexistence region. A simple phenomenological theory is developed to illustrate this idea, and several experimentally testable consequences are discussed. Shear is shown to enhance the kinetic role of the hidden binodal.
The conformational statistics of ring polymers in melts or dense solutions is strongly affected by their quenched microscopic topological state. The effect is particularly strong for non-concatenated unknotted rings, which are known to crumple and segregate and which have been implicated as models for the generic behavior of interphase chromosomes. Here we use a computationally efficient multi-scale approach to show that melts of rings of total contour length $L_r$ can be {\it quantitatively} mapped onto melts of {\em interacting} lattice trees with gyration radii $\langle R_g^2(L_r) \rangle \…
We present computer simulations of a dynamic Monte Carlo algorithm for polymer chains on the FCC lattice which takes explicitly 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 to standard melts of unknotted and unconcatenated rings, our simulation…
We present molecular dynamics simulations of a simple model for polymer melts with intramolecular barriers. We investigate structural relaxation as a function of the barrier strength. Dynamic correlators can be consistently analyzed within the framework of the Mode Coupling Theory (MCT) of the glass transition. Control parameters are tuned in order to induce a competition between general packing effects and polymer-specific intramolecular barriers as mechanisms for dynamic arrest. This competition yields unusually large values of the so-called MCT exponent parameter and rationalize qualitative…
Despite the long-recognized fact that chemical structure and specific interactions greatly influence the thermodynamic properties of polymer systems, a predictive molecular theory that enables systematically addressing the role of chemical structure and specific interactions has been slow to develop even for polymer melts. While the lattice cluster theory (LCT) provides a powerful vehicle for understanding the influence of various molecular factors, such as monomer structure, on the thermodynamic properties of polymer melts and blends, the application of the LCT has heretofore been limited to …
We introduce a mesoscale technique for simulating the structure and rheology of block copolymer melts and blends in hydrodynamic flows. The technique couples dynamic self consistent field theory (DSCFT) with continuum hydrodynamics and flow penalization to simulate polymeric fluid flows in channels of arbitrary geometry. We demonstrate the method by studying phase separation of an ABC triblock copolymer melt in a sub-micron channel with neutral wall wetting conditions. We find that surface wetting effects and shear effects compete, producing wall-perpendicular lamellae in the absence of flow, …
The dynamics of ring polymer melts are studied via molecular dynamics simulations of the Kremer-Grest bead-spring model. Rouse mode analysis is performed in comparison with linear polymers by changing the chain length. Rouse-like behavior is observed in ring polymers by quantifying the chain length dependence of the Rouse relaxation time, whereas a crossover from Rouse to reptation behavior is observed in linear polymers. Furthermore, the non-Gaussian parameters of the monomer bead displacement and chain center-of-mass displacement are analyzed. It is found that the non-Gaussianity of ring pol…
In the past twenty years, shear-banding flows have been probed by various techniques, such as rheometry, velocimetry and flow birefringence. In micellar solutions, many of the data collected exhibit unexplained spatio-temporal fluctuations. Recently, it has been suggested that those fluctuations originate from a purely elastic instability of the flow. In cylindrical Couette geometry, the instability is reminiscent of the Taylor-like instability observed in viscoelastic polymer solutions. In this letter, we describe how the criterion for purely elastic Taylor-Couette instability should be adapt…
Significant progress was made in recent years in the understanding of the proton spin kinetics in polymer melts. Generally, the proton spin kinetics is determined by intramolecular and intermolecular magnetic dipole-dipole contributions of proton spins. During many decades it was postulated that the main contribution is a result of intramolecular magnetic dipole-dipole interactions of protons belonging to the same polymer segment. It appears that this postulate is far from reality. The relative weights of intra- and intermolecular contributions are time dependent and sensitive to details of po…
Molecular dynamics simulations were conducted to investigate the structural properties of melts of nonconcatenated ring polymers and compared to melts of linear polymers. The longest rings were composed of N=1600 monomers per chain which corresponds to roughly 57 entanglement lengths for comparable linear polymers. For the rings, the radius of gyration squared was found to scale as N to the 4/5 power for an intermediate regime and N to the 2/3 power for the larger rings indicating an overall conformation of a crumpled globule. However, almost all beads of the rings are "surface beads" interact…
The COMOFLO dynamic Monte Carlo algorithm is extended to enable the simulation of steady-state extensional rheology of dense melts for the first time ever. This significant advancement provides the ability to accurately capture the extensional viscosity of entangled polymer melts from low deformation rates, throughout the strain hardening regime, and into the region of viscosity thinning To do so, the purely extensional flow field associated with a four roll mill experiment is implemented in three dimensions. Periodic boundary conditions exist in all directions to enable a uniform deformation …
Molecular dynamics simulations were conducted to investigate the dynamic properties of melts of nonconcatenated ring polymers and compared to melts of linear polymers. The longest rings were composed of N=1600 monomers per chain which corresponds to roughly 57 entanglement lengths for comparable linear polymers. The ring melts were found to diffuse faster than their linear counterparts, with the self-diffusion coefficient for both architectures scaling as approximately N to the -2.4 power for large N. The mean-square displacement of the center-of-mass of the rings follows a sub-diffusive behav…
We present an effective and simple multiscale method for equilibrating Kremer Grest model polymer melts of varying stiffness. In our approach, we progressively equilibrate the melt structure above the tube scale, inside the tube and finally at the monomeric scale. We make use of models designed to be computationally effective at each scale. Density fluctuations in the melt structure above the tube scale are minimized through a Monte Carlo simulated annealing of a lattice polymer model. Subsequently the melt structure below the tube scale is equilibrated via the Rouse dynamics of a force-capped…
Using molecular dynamics simulations of a tangent-soft-sphere bead-spring polymer model, we examine the degree to which semiflexible polymer melts solidify at isostaticity. Flexible and stiff chains crystallize when they are isostatic as defined by appropriate degree-of-freedom-counting arguments. Semiflexible chains also solidify when isostatic if a generalized isostaticity criterion that accounts for the slow freezing out of configurational freedom as chain stiffness increases is employed. The dependence of the average coordination number at solidification $Z(T_s)$ on chains' characteristic …
A strategy is developed for generating equilibrated high molecular-weight polymer melts described with microscopic detail by sequentially backmapping coarse-grained (CG) configurations. The microscopic test model is generic but retains features like hard excluded volume interactions and realistic melt densities. The microscopic representation is mapped onto a model of soft spheres with fluctuating size, where each sphere represents a microscopic subchain with $N_{\rm b}$ monomers. By varying $N_{\rm b}$ a hierarchy of CG representations at different resolutions is obtained. Within this hierarc…
