Polyelectrolyte complexes are omnipresent both in nature and the technological world, including nucleotide condensates, biological marine adhesives, food stabilizers, encapsulants, carriers for gene therapy. However, true phase behavior of complexes, resulting from associative separation oppositely charged polyelectrolytes, remains poorly understood. Here, we rely on complementary experimental simulation approaches to create a complete quantitative description polyelectrolyte that represents...

It is widely appreciated that the addition of salts to water leads significant changes in thermodynamic and dynamic properties these aqueous solutions have great significance biology manufacturing applications. However, no theoretical framework currently exists describes property an internally consistent fashion. In previous work, we developed a coarse-grained model electrolyte capable reproducing basic trends on how influence viscosity diffusion coefficient. The present work explores...

Abstract Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (<1% by mass) has been observed in scattering experiments and molecular dynamics simulations. Here we show that contrast to uncharged, amphiphilic block copolymers form discrete micelles enter a phase strongly interacting gradual manner with increasing concentration, the formation dilute individual is prevented polyelectrolyte complexation-driven assembly...

Ion-specific solvation has fundamental implications in biochemistry, and the thermodynamics dynamics of aqueous salt solutions have correspondingly been investigated intensively. Nonetheless, there are unresolved issues modeling related problem polymers dissolved these solutions. In particular, experiments show that self-diffusion coefficient, D, water molecules electrolyte can be either enhanced or suppressed by particular salts having same valence where observed changes correlate with...

The discrete slip-link model (DSM) was developed to describe the dynamics of flexible polymer melts. is able predict linear viscoelasticity monodisperse linear, polydisperse and branched systems. also shows good agreement with dielectric relaxation experiments, except for single data set available bidisperse systems a small volume fraction long chains. In this work, both shear elongational flow predictions obtained using DSM without parameter adjustment are shown. Model agree very well...

Complex coacervation refers to the formation of distinct liquid phases that arise when polyelectrolytes are mixed under appropriate polymer and salt concentrations. Molecular-level studies have been limited. In this work, a coarse-grained model polymers corresponding counterions is proposed used simulate as function length overall concentration. Several sampling methods determine phase behavior underlying polymers. particular, results simulations in different ensembles shown be consistent...

A theoretically informed entangled polymer simulation approach is presented for description of the linear and non-linear rheology melts. The relies on a many-chain representation introduces topological effects that arise from non-crossability molecules through effective fluctuating interactions, mediated by slip-springs, between neighboring pairs macromolecules. total number slip-springs not preserved but, instead, it controlled chemical potential determines average molecular weight...

Coarse grained simulation approaches provide powerful tools for the prediction of equilibrium properties polymeric systems. Recent efforts have sought to develop coarse-graining strategies capable predicting non-equilibrium behavior entangled materials. Slip-link and slip-spring models, in particular, been shown be reproducing several key aspects linear response rheology polymer melts. In this work, we extend a previously proposed multi-chain model way that correctly incorporates effects...

Views Icon Article contents Figures & tables Video Audio Supplementary Data Peer Review Share Twitter Facebook Reddit LinkedIn Tools Reprints and Permissions Cite Search Site Citation Marat Andreev, Hualong Feng, Ling Yang, Jay D. Schieber; Universality speedup in equilibrium nonlinear rheology predictions of the fixed slip-link model. J. Rheol. 1 May 2014; 58 (3): 723–736. https://doi.org/10.1122/1.4869252 Download citation file: Ris (Zotero) Reference Manager EasyBib Bookends Mendeley...

Dielectric spectroscopy is often used as a tool complementary to rheology for investigation of relaxation processes viscoelastic medium. In particular, dielectric type-A polymers reveals the autocorrelation function end-to-end vector chain, whereas modulus stress, which depends on more-local structural moments chain conformation. Here we examine published data monodisperse linear, bidisperse linear and star-branched polyisoprene using discrete slip-link model (DSM). Although DSM makes...

The flow-induced crystallization of polymers is a ubiquitous aspect processing where the effect flow can dramatically alter end-use properties polymers. Here, we will describe development new methodology whereby on kinetics in polyethylene be determined after has occurred. This first illustration for rapidly crystallizing polyethylene, which required different approach than what been done other materials. Critically, this necessitated an understanding self-nucleation and melt memory behavior...

Despite strong industrial interest, only recently have quantitative predictions for entangled polymer rheology become possible. Major advances are achieved with an alternative approach to entanglement modeling—slip-links. For example, the discrete slip-link model (DSM) allows equilibrium and high-flow-rate a connection molecular basis. Slip-link models applicable arbitrary composition chain architectures, but usually incur high numerical cost. Recent in coarse-graining allowed speedup of...

The discrete slip-link theory is a hierarchy of strongly connected models that have great success predicting the linear and nonlinear rheology high-molecular-weight polymers. Three four parameters most-detailed model, which can be extracted from primitive-path analysis, give quantitative agreement with experimental data for all examined chemistries (polystyrene, polyisoprene, polybutadiene, polyethylene). Here, we attempt to extract remaining friction parameter atomistic simulations. In...

A microscopic molecular model of polymeric molecules that captures the effects topological constraints is used to consider how microphase segregation can alter distribution entanglements both in space and along chain contours. Such are obtained by using Z1 algorithm, it found for diblock copolymers lamellar morphology they not homogeneously distributed, but instead exhibit a spatial dependence as consequence self-organization polymer blocks. The specific shape inhomogeneous affected weight...

We propose a simulation tool that can predict the macroscopic properties of entangled polymers during and after processing, using molecular model whose parameters are determined from first principles.

The mechanical properties of a cross‐linked polydimethylsiloxane (PDMS) network swollen with nonreactive entangled PDMS solvent was previously studied experimentally. In this article, we use the discrete slip‐link model to predict its linear and nonlinear rheology. Model parameters are obtained from dynamic modulus data pure solvent. Network rheology predictions also require an estimate fraction architecture dangling or inactive strands in network, which is not directly measurable. active...

Many industrial polymer melts are entangled and undergo crystallization during processing. Several recent studies have reported experimental data for the rheology of crystallizing polymers. Meanwhile, over past few years, slip-link models been demonstrated to describe under a variety nonlinear deformation conditions. In this work, we present modification model an melt undergoing crystallization. The partially crystallized is represented by blend linear chains with free ends cross-linked,...

Polymer crystallization occurs in many plastic manufacturing processes, from injection molding to film blowing. Linear low-density polyethylene (LLDPE) is one of the most commonly processed polymers, wherein type and extent short-chain branching (SCB) may be varied influence crystallization. In this work, we report simultaneous measurements rheology Raman spectra, using a Rheo-Raman microscope, for two industrial-grade LLDPEs undergoing These polymers are characterized by broad...

We evaluate the thermodynamic consistency of anisotropic mobile slip-link model for entangled flexible polymers. The level description is that a single chain, whose interactions with other chains are coarse grained to discrete entanglements. dynamics consist motion entanglements through space and chain entanglements, as well creation destruction which implemented in mean-field way. Entanglements modeled slip links, spatial positions confined by quadratic potentials. confinement potentials...

The Wiener-Khinchin theorem for the Fourier-Laplace transformation (WKT-FLT) provides a robust method to obtain single-side Fourier transforms of arbitrary time-domain relaxation functions (or autocorrelation functions). Moreover, by combining an on-the-fly algorithm with WKT-FLT, numerical calculations various complex spectroscopic data in wide frequency range become significantly more efficient. However, discretized WKT-FLT equation, obtained simply replacing integrations discrete...

A computational and experimental framework for quantifying flow-enhanced nucleation (FEN) in polymers is presented demonstrated an industrial-grade linear low-density polyethylene (LLDPE). Experimentally, kinetic measurements of isothermal crystallization were performed by using fast-scanning calorimetry (FSC) melts that presheared at various strain rates. The effect shear on the average conformation tensor melt was modeled with discrete slip-link model (DSM). then related to acceleration...