Self-Consistent-Field Study of Adsorption and Desorption Kinetics of Polyethylene Melts on Graphite and Comparison with Atomistic Simulations

A method is formulated, based on combining self-consistent field theory with dynamically corrected transition state theory, for estimating the rates of adsorption and desorption of end-constrained chains (e.g. by crosslinks or entanglements) from a polymer melt onto a solid substrate. This approach is tested on a polyethylene/graphite system, where the whole methodology is parametrized by atomistically detailed molecular simulations. For short-chain melts, which can still be addressed by molecular dynamics simulations with reasonable computational resources, the self-consistent field approach gives predictions of the adsorption and desorption rate constants which are gratifyingly close to molecular dynamics estimates.Comment: 18 pages, 10 figure

Equation of State Based Slip Spring Model for Entangled Polymer Dynamics

A mesoscopic, mixed particle- and field-based Brownian dynamics methodology for the simulation of entangled polymer melts has been developed. Polymeric beads consist of several Kuhn segments, and their motion is dictated by the Helmholtz energy of the sample, which is a sum of the entropic elasticity of chain strands between beads, slip springs, and nonbonded interactions. The entanglement effect is introduced by the slip springs, which are springs connecting either nonsuccessive beads on the same chain or beads on different polymer chains. The terminal positions of slip springs are altered during the simulation through a kinetic Monte Carlo hopping scheme, with rate-controlled creation/destruction processes for the slip springs at chain ends. The rate constants are consistent with the free energy function employed and satisfy microscopic reversibility at equilibrium. The free energy of nonbonded interactions is derived from an appropriate equation of state, and it is computed as a functional of the local density by passing an orthogonal grid through the simulation box; accounting for it is necessary for reproducing the correct compressibility of the polymeric material. Parameters invoked by the mesoscopic model are derived from experimental volumetric and viscosity data or from atomistic molecular dynamics simulations, establishing a "bottom-up" predictive framework for conducting slip spring simulations of polymeric systems of specific chemistry. The mesoscopic simulation methodology is implemented for the case of cis-1,4-polyisoprene, whose structure, dynamics, thermodynamics, and linear rheology in the melt state are quantitatively predicted and validated without a posteriori fitting the results to experimental measurements.Comment: 80 pages, 17 figure

Fine-time energetic electron behavior observed by Cluster/RAPID in the magnetotail associated with X-line formation and subsequent current disruption

Energetic electrons with 90deg pitch angle have been observed in the magnetotail at ~19 <i>R<sub>E</sub></i> near local midnight during the recovery phase of a substorm event on 27 August 2001 (Baker et al., 2002). Based on auroral images Baker et al. (2002) placed the substorm expansion phase between ~04:06:16 and ~04:08:19 UT. The electron enhancements perpendicular to the ambient magnetic field occurred while the Cluster spacecraft were on closed field lines in the central plasma sheet approaching the neutral sheet. Magnetic field and energetic particle measurements have been employed from a number of satellites, in order to determine the source and the subsequent appearance of these electrons at the Cluster location. It is found that ~7.5 min after an X-line formation observed by Cluster (Baker et al., 2002) a current disruption event took place inside geosynchronous orbit and subsequently expanded both in local time and tailward, giving rise to field-aligned currents and the formation of a current wedge. A synthesis of tail reconnection and the cross-tail current disruption scenario is proposed for the substorm global initiation process: When a fast flow with northward magnetic field, produced by magnetic reconnection in the midtail, abruptly decelerates at the inner edge of the plasma sheet, it compresses the plasma populations earthward of the front, altering dynamically the B<sub>z</sub> magnetic component in the current sheet. This provides the necessary and sufficient conditions for the kinetic cross-field streaming/current (KCSI/CFCI) instability (Lui et al., 1990, 1991) to initiate. As soon as the ionospheric conductance increases over a threshold level, the auroral electrojet is greatly intensified (see Fig. 2 in Baker et al., 2002), which leads to the formation of the substorm current wedge and dipolarization of the magnetic field. This substorm scenario combines the near-Earth neutral line and the current disruption for the initiation of substorms, at least during steady southward IMF. One can conclude the following: The observations suggest that the anisotropic electron increases observed by Cluster are not related to an acceleration mechanism associated with the X-line formation in the midtail, but rather these particles are generated in the dusk magnetospheric sector due to the longitudinal and tailward expansion of a current disruption region and subsequently observed at the Cluster location with no apparent energy dispersion.<br><br> <b>Keywords.</b> Magnetospheric physics (Magnetotail; Plasma convection; Storms and substorms

Network dynamics:a computational framework for the simulation of the glassy state

An out-of-equilibrium simulation method for tracking the time evolution of glassy systems (or any other systems that can be described by hopping dynamics over a network of discrete states) is presented. Graph theory and complexity concepts are utilised, alongside the method of the dynamical integration of a Markovian web (G. C. Boulougouris and D. N. Theodorou, J. Chem. Phys., 2007, 127, 084903) in order to provide a unified framework for dealing with the long time-scales of non-ergodic systems. Within the developed formalism, the network of states accessible to the system is considered a finite part of the overall universe, communicating with it through well-defined boundary states. The analytical solution of the probability balance equation proceeds without the need for assuming the existence of an equilibrium distribution among the states of the network and the corresponding survival and escape probabilities (as functions of time) are defined. More importantly, the study of the probability flux through the dividing surface separating the system and its environment reveals the relaxation mechanisms of the system. We apply our approach to the network of states obtained by exploring the energy landscape of an atomistically detailed glassy specimen of atactic polystyrene. The rate constants connecting different basins of the landscape are evaluated by multi-dimensional transition-state-theory. We are able to accurately probe the appearance of the δ- and γ-subglass relaxation mechanisms and their relevant time-scales, out of atomistic simulations. The proposed approach can fill a gap in the rational molecular design toolbox, by providing an alternative to molecular dynamics for structural relaxation in glasses and/or other slow molecular processes (e.g., adsorption or desorption) that involve very distant time-scales.</p

Molecular Dynamics Test of the Stress-Thermal Rule in Polyethylene and Polystyrene Entangled Melts

Anisotropic thermal transport induced by deformation and the linear relation between the thermal conductivity and stress tensors, also known as the stress-thermal rule (STR), are tested via molecular dynamics simulations in well-entangled linear polyethylene (PE) and polystyrene (PS) melts subjected to extensional flow. We propose a method to determine the stress in deformed molecular melts, a key component missing in prior simulation studies on thermal transport in polymers that prevented verification of the STR. We compare our results with available data from previous experimental and simulation studies. Thermal conductivity (TC) is found to increase (decrease) in the direction parallel (perpendicular) to the imposed stretch. We find that the STR is valid for both PE and PS over a wide range of deformation rates and stress levels. In direct agreement with experimental evidence and the STR, we observe that for a given strain, the anisotropy in TC increases with the strain rate. Surprisingly, our results for PE question the universal behavior with respect to polymer chemistry suggested by experiments by showing a significantly higher proportionality constant (the stress-thermal coefficient) between stress and anisotropy in TC. We argue that this discrepancy can be explained by the high degree of entanglement interactions in PE affecting the transport of energy at the molecular level. Our conjecture is tested by studying an entangled linear PS melt, a polymer with a much lower entanglement plateau, for which thermal transport experimental results are available. For PS, the normalized stress-thermal coefficient is found to be commensurate with the experimental value. Finally, we test the fundamental molecular hypothesis of preferential energy transport along the backbone of polymer chains used to formulate the STR, which was prompted by early experimental evidence showing an increase in TC with chain length. We are able to establish that the increase in TC with chain length in PE melts fades as the system becomes entangled (i.e., TC remains constant beyond the critical entanglement chain length that marks the transition to entanglement-dominated rheological behavior). Our findings are of key importance in developing robust molecular-to-continuum methodologies for the study of nonisothermal macroscopic flows that are extremely relevant to polymer manufacturing processes.European Union’s Horizon 2020 research and innovation program under the Marie Skłodowska-Curie IF MTCIATTP 750985

Mesoscopic simulations of crosslinked polymer networks

Institut für Theoretische Physik, Georg-August Universität, Göttingen, Germany E-mail: [email protected] Abstract. A new methodology and the corresponding C++ code for mesoscopic simulations of elastomers are presented. The test system, crosslinked cis-1,4-polyisoprene, is simulated with a Brownian Dynamics/kinetic Monte Carlo algorithm as a dense liquid of soft, coarse-grained beads, each representing 5-10 Kuhn segments. From the thermodynamic point of view, the system is described by a Helmholtz free-energy containing contributions from entropic springs between successive beads along a chain, slip-springs representing entanglements between beads on different chains, and non-bonded interactions. The methodology is employed for the calculation of the stress relaxation function from simulations of several microseconds at equilibrium, as well as for the prediction of stress-strain curves of crosslinked polymer networks under deformation. Introduction Atomistic and mesoscopic simulations are widely employed for the study of polymer systems, since they provide insights that are complementary to the information derived from experiments. Although the full-atom or united-atom representations provide an accurate description of polymers, their long relaxation time constitutes a severe obstacle to such approaches, and thus the development of mesoscopic (or coarse-grained) models is needed to cover longer time and length scales. One of the main characteristics of polymer melts and polymer networks is the entanglement effect, arising due to the uncrossability of polymer chains, which gives rise to complicated topological constraints [1]-[4]. The tube model, which considers a single chain in a mean field, is one of the most significant models for the description of entangled polymer