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Register a new userScale-free static and dynamical correlations in melts of monodisperse and Flory-distributed homopolymers: A review of recent bond-fluctuation model studies
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It has been assumed until very recently that all long-range correlations are screened in three-dimensional melts of linear homopolymers on distances beyond the correlation length $xi$ characterizing the decay of the density fluctuations. Summarizing simulation results obtained by means of a variant of the bond-fluctuation model with finite monomer excluded volume interactions and topology violating local and global Monte Carlo moves, we show that due to an interplay of the chain connectivity and the incompressibility constraint, both static and dynamical correlations arise on distances $r gg xi$. These correlations are scale-free and, surprisingly, do not depend explicitly on the compressibility of the solution. Both monodisperse and (essentially) Flory-distributed equilibrium polymers are considered.
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By Monte Carlo simulations of a variant of the bond-fluctuation model without topological constraints we examine the center-of-mass (COM) dynamics of polymer melts in $d=3$ dimensions. Our analysis focuses on the COM displacement correlation function $CN(t) approx partial_t^2 MSDcmN(t)/2$, measuring the curvature of the COM mean-square displacement $MSDcmN(t)$. We demonstrate that $CN(t) approx -(RN/TN)^2 (rhostar/rho) f(x=t/TN)$ with $N$ being the chain length ($16 le N le 8192$), $RNsim N^{1/2}$ the typical chain size, $TNsim N^2$ the longest chain relaxation time, $rho$ the monomer density, $rhostar approx N/RN^d$ the self-density and $f(x)$ a universal function decaying asymptotically as $f(x) sim x^{-omega}$ with $omega = (d+2) times alpha$ where $alpha = 1/4$ for $x ll 1$ and $alpha = 1/2$ for $x gg 1$. We argue that the algebraic decay $N CN(t) sim - t^{-5/4}$ for $t ll TN$ results from an interplay of chain connectivity and melt incompressibility giving rise to the correlated motion of chains and subchains.
The classical bond-fluctuation model (BFM) is an efficient lattice Monte Carlo algorithm for coarse-grained polymer chains where each monomer occupies exclusively a certain number of lattice sites. In this paper we propose a generalization of the BFM where we relax this constraint and allow the overlap of monomers subject to a finite energy penalty $overlap$. This is done to vary systematically the dimensionless compressibility $g$ of the solution in order to investigate the influence of density fluctuations in dense polymer melts on various s tatic properties at constant overall monomer density. The compressibility is obtained directly from the low-wavevector limit of the static structure fa ctor. We consider, e.g., the intrachain bond-bond correlation function, $P(s)$, of two bonds separated by $s$ monomers along the chain. It is shown that the excluded volume interactions are never fully screened for very long chains. If distances smaller than the thermal blob size are probed ($s ll g$) the chains are swollen acc ording to the classical Fixman expansion where, e.g., $P(s) sim g^{-1}s^{-1/2}$. More importantly, the polymers behave on larger distances ($s gg g$) like swollen chains of incompressible blobs with $P(s) si m g^0s^{-3/2}$.
Following the Flory ideality hypothesis intrachain and interchain excluded volume interactions are supposed to compensate each other in dense polymer systems. Multi-chain effects should thus be neglected and polymer conformations may be understood from simple phantom chain models. Here we provide evidence against this phantom chain, mean-field picture. We analyze numerically and theoretically the static correlation function of the Rouse modes. Our numerical results are obtained from computer simulations of two coarse-grained polymer models for which the strength of the monomer repulsion can be varied, from full excluded volume (`hard monomers) to no excluded volume (`phantom chains). For nonvanishing excluded volume we find the simulated correlation function of the Rouse modes to deviate markedly from the predictions of phantom chain models. This demonstrates that there are nonnegligible correlations along the chains in a melt. These correlations can be taken into account by perturbation theory. Our simulation results are in good agreement with these new theoretical predictions.
Due to the potential impact on the diagnosis and treatment of various cardiovascular diseases, work on the rheology of blood has significantly expanded in the last decade, both experimentally and theoretically. Experimentally, blood has been confirmed to demonstrate a variety of non-Newtonian rheological characteristics, including pseudoplasticity, viscoelasticity, and thixotropy. New rheological experiments and the development of more controlled experimental protocols on more extensive, broadly physiologically characterized, human blood samples demonstrate the sensitivity of aspects of hemorheology to several physiological factors. For example, at high shear rates to the red blood cells elastically deformation, imparting viscoelasticity, while and at low shear rates, they form rouleaux structures that impart additional, thixotropic behavior. In addition to these advances in experimental methods and validated data sets, significant advances have also been made in both microscopic simulations and macroscopic, continuum, modeling, as well as novel, multiscale approaches. We outline and evaluate the most promising of these recent advances. Although we primarily focus on human blood rheology, we also discuss recent observations on variations across some animal species that provide some indication on evolutionary effects.
We present a numerical study of the slip link model introduced by Likhtman for describing the dy- namics of dense polymer melts. After reviewing the technical aspects associated with the implemen- tation of the model, we extend previous work in several directions. The dependence of the relaxation modulus with the slip link density and the slip link stiffness is reported. Then the nonlinear rheolog- ical properties of the model, for a particular set of parameters, are explored. Finally, we introduce excluded volume interactions in a mean field such as manner in order to describe inhomogeneous systems, and we apply this description to a simple nanocomposite model. With this extension, the slip link model appears as a simple and generic model of a polymer melt, that can be used as an alternative to molecular dynamics for coarse grained simulations of complex polymeric systems.
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