Comparison of Dissipative Particle Dynamics and Langevin thermostats for out-of-equilibrium simulations of polymeric systems

In this work we compare and characterize the behavior of Langevin and Dissipative Particle Dynamics (DPD) thermostats in a broad range of non-equilibrium simulations of polymeric systems. Polymer brushes in relative sliding motion, polymeric liquids in Poiseuille and Couette flows, and brush-melt interfaces are used as model systems to analyze the efficiency and limitations of different Langevin and DPD thermostat implementations. Widely used coarse-grained bead-spring models under good and poor solvent conditions are employed to assess the effects of the thermostats. We considered equilibrium, transient, and steady state examples for testing the ability of the thermostats to maintain const…

On the tribology and rheology of polymer brushes in good solvent conditions: a molecular dynamics study

Tribological and rheological properties of two polymer brushes in relative sliding motion and good solvent conditions are investigated by means of molecular dynamics (MD) simulations. The lateral forces between the brushes are found to decrease logarithmically with increasing relative sliding velocity v0 over a range of more than one decade in v0. We also observe an almost logarithmic relaxation of the end-to-end distance vector that occurs after sliding is stopped. The coincidence of these logarithmic dependencies support the picture that friction between polymer brushes is small due to the retraction of the polymers from the interpenetration zone. The shear stress relaxes almost instantly…

Nonlinear effects in charge stabilized colloidal suspensions

Molecular Dynamics simulations are used to study the effective interactions in charged stabilized colloidal suspensions. For not too high macroion charges and sufficiently large screening, the concept of the potential of mean force is known to work well. In the present work, we focus on highly charged macroions in the limit of low salt concentrations. Within this regime, nonlinear corrections to the celebrated DLVO theory [B. Derjaguin and L. Landau, Acta Physicochem. USSR {\bf 14}, 633 (1941); E.J.W. Verwey and J.T.G. Overbeck, {\em Theory of the Stability of Lyotropic Colloids} (Elsevier, Amsterdam, 1948)] have to be considered. For non--bulklike systems, such as isolated pairs or triples…

Molecular Simulation of Polymer Melts and Blends: Methods, Phase Behavior, Interfaces, and Surfaces

Conformational Properties of End-Grafted Bottlebrush Polymers

Scaling analysis combined with free-energy calculations and molecular dynamics simulations of a coarse-grained bead-spring model have been used to study the structural properties of planar brushes ...

Polydispersity Effects on Interpenetration in Compressed Brushes

We study the effect of polydispersity on the compression and interpenetration properties of two opposing polymer brushes by numerical self-consistent field approach and by analytical theory. Polydispersity is represented by an experimentally relevant Schulz–Zimm chain-length distribution. We focus on three different polydispersities representing sharp, moderate, and extremely wide chain length distributions and derive approximate analytical expressions for the pressure–separation curves, Π(D). We study the brush interpenetration and quantify it in terms of the overlap integral, Γ, representing the number of interbrush contacts, and interpenetration length, δ. For the case of moderate densit…

Frictional drag between polymer bearing surfaces

Some fundamental features of friction between two polymer bearing surfaces in relative sliding motion are investigated by molecular dynamics simulations. End-tethered and adsorbed polymers are considered under good and poor solvent conditions. The shear stress is measured while varying the solvent's viscosity, surface separation, degree of polymerization and grafting density. For all systems we observe shear thinning that is attributed to the orientation of the chains along the shear direction. This effect is particularly strong for brushes, for which the shear stress during the steady sliding state is mainly determined by the degree of overlap between the brushes.

Polymer-brush lubricated surfaces with colloidal inclusions under shear inversion.

We characterize the response of compressed, sheared polymer-brush bilayers with colloidal inclusions to highly nonstationary inversion processes by means of molecular dynamics simulations and scaling theory. Bilayers with a simple (dimeric) solvent reveal an overshoot for the shear stress, while simulations of dry brushes without explicit solvent molecules fail to display this effect. We demonstrate that mechanical instabilities can be controlled by the inclusion of macromolecular structures, such as colloids of varying softness. Based on a recently developed theory, we suggest a scaling approach to determine a characteristic time for conformational and collective responses.

Polymer brushes under flow and in other out-of-equilibrium conditions

Polymer brushes are formed from flexible linear macromolecules tethered at one chain end to a solid substrate, forming a dense polymeric layer of polymer chains which are more or less stretched in the direction perpendicular to the substrate surface. These systems find interest also due to numerous applications (colloid stabilization, improvement of lubrication properties when the surfaces are exposed to shear, protection of the surface against adsorption of nanoparticles or proteins, etc.), for which often the dynamic non-equilibrium response of these brushes to external perturbation is important. The present review summarizes recent computer simulation studies pertinent to these questions…

Frictional Forces between Strongly Compressed, Nonentangled Polymer Brushes: Molecular Dynamics Simulations and Scaling Theory

By means of molecular dynamics simulations and scaling theory we study the response of opposing polymer brushes to constant shear motion under good solvent conditions. Model systems that contain explicit solvent molecules (Lennard-Jones dimers) are compared to solvent-free systems while varying of the distance between the grafted layers and their molecular parameters, chain length and grafting density. Our study reveals a power-law dependence of macroscopic transport properties on the Weissenberg number, W, beyond linear response. For instance, we find that the kinetic friction constant scales as μ ∼ W0.57 for large values of W. We develop a scaling theory that describes our data and previo…

Frictional Drag Mechanisms between Polymer-Bearing Surfaces

The fundamental features of friction between two polymer-bearing surfaces in relative sliding motion are investigated by molecular dynamics simulation. Adsorbed and grafted polymers are considered in good and bad solutions. The solvent is not treated explicitly but indirectly in terms of a Langevin thermostat. In both systems, we observe shear thinning that is attributed to an orientation of the radius of gyration along the sliding direction. This effect is particularly strong for surfaces bearing polymer brushes. In this case, the shear stresses are mainly determined by the degree of the interpenetration of brushes.

Qualitative characterisation of effective interactions of charged spheres on different levels of organisation using Alexander’s renormalised charge as reference

Abstract Effective interactions are conveniently determined from experimental or numerical data by fitting a Debye–Huckel potential with an effective charge Z ∗ and an effective electrolyte concentration c ∗ as free parameters. In this contribution we numerically solved the Poisson–Boltzmann equation to obtain the so-called renormalised charge Z PBC ∗ . For sufficiently large bare charge Z one finds a saturation of Z ∗ which scales as Z ∗ = A a / λ B , where a is the particle radius, λ B the Bjerrum length and A a proportionality factor of order (8–10). The saturation value increases with increased total micro-ion concentration and shows a shallow minimum as a function of packing fraction. …

Static properties of end-tethered polymers in good solution: A comparison between different models

We present a comparison between results, obtained from different simulation models, for the static properties of end-tethered polymer layers in good solvent. Our analysis includes data from two previous studies--the bond fluctuation model of Wittmer et al. [J. Chem. Phys. 101, 4379 (1994)] and the off-lattice bead-spring model of Grest and Murat [Macromolecules 26, 3108 (1993)]. Additionally, we explore the properties of a similar off-lattice model simulated close to the Theta temperature. We show that the data for the bond fluctuation and the Grest-Murat model can be analyzed in terms of scaling theory because chains are swollen inside the Pincus blob. In the vicinity of the Theta point th…