Experiments and Modeling of Flow-Enhanced Nucleation in LLDPE.

A computational and experimental framework for quantifying flow-enhanced nucleation (FEN) in polymers is presented and demonstrated for an industrial-grade linear low-density polyethylene (LLDPE). Experimentally, kinetic measurements of isothermal crystallization were performed by using fast-scanning calorimetry (FSC) for melts that were presheared at various strain rates. The effect of shear on the average conformation tensor of the melt was modeled with the discrete slip-link model (DSM). The conformation tensor was then related to the acceleration in nucleation kinetics by using an expression previously validated with nonequilibrium molecular dynamics (NEMD). The expression is based on the nematic order tensor of Kuhn segments, which can be obtained from the conformation tensor of entanglement strands. The single adjustable parameter of the model was determined by fitting to the experimental FSC data. This expression accurately describes FEN for the LLDPE, representing a significant advancement toward the development of a fully integrated processing model for crystallizable polymers.

Thermodynamically consistent incorporation of entanglement spatial fluctuations in the slip-link model.

We evaluate the thermodynamic consistency of the anisotropic mobile slip-link model for entangled flexible polymers. The level of description is that of a single chain, whose interactions with other chains are coarse grained to discrete entanglements. The dynamics of the model consist of the motion of entanglements through space and of the chain through the entanglements, as well as the creation and destruction of entanglements, which are implemented in a mean-field way. Entanglements are modeled as discrete slip links, whose spatial positions are confined by quadratic potentials. The confinement potentials move with the macroscopic velocity field, hence the entanglements fluctuate around purely affine motion. We allow for anisotropy of these fluctuations, described by a set of shape tensors. By casting the model in the form of the general equation for the nonequilibrium reversible-irreversible coupling from nonequilibrium thermodynamics, we show that (i) since the confinement potentials contribute to the chain free energy, they must also contribute to the stress tensor, (ii) these stress contributions are of two kinds: one related to the virtual springs connecting the slip links to the centers of the confinement potentials and the other related to the shape tensors, and (iii) these two kinds of stress contributions cancel each other if the confinement potentials become anisotropic in flow, according to a lower-convected evolution of the confinement strength or, equivalently, an upper-convected evolution of the shape tensors of the entanglement spatial fluctuations. In previous publications, we have shown that this cancellation is necessary for the model to obey the stress-optical rule and the Green-Kubo relation, and simultaneously to agree with plateau modulus predictions of multichain models and simulations.

Rheology of Crystallizing LLDPE.

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 the type and extent of short-chain branching (SCB) may be varied to influence crystallization. In this work, we report simultaneous measurements of the rheology and Raman spectra, using a Rheo-Raman microscope, for two industrial-grade LLDPEs undergoing crystallization. These polymers are characterized by broad polydispersity, SCB and the presence of polymer chain entanglements. The rheological behavior of these entangled LLDPE melts is modeled as a function of crystallinity using a slip-link model. The partially crystallized melt is represented by a blend of linear chains with either free or crosslinked ends, wherein the crosslinks represent attachment to growing crystallites, and a modulus shift factor that increases with degree of crystallinity. In contrast to our previous application of the slip-link model to isotactic polypropylene (iPP), in which the introduction of only bridging segments with crosslinks at both ends was sufficient to describe the available data, for these LLDPEs we find it necessary to introduce dangling segments, with crosslinks at only one end. The model captures quantitatively the evolution of viscosity and elasticity with crystallization over the whole range of frequencies in the linear regime for two LLDPE grades.

Spectroscopic analysis in molecular simulations with discretized Wiener-Khinchin theorem for Fourier-Laplace transformation.

The Wiener-Khinchin theorem for the Fourier-Laplace transformation (WKT-FLT) provides a robust method to obtain the single-side Fourier transforms of arbitrary time-domain relaxation functions (or autocorrelation functions). Moreover, by combining an on-the-fly algorithm with the WKT-FLT, the numerical calculations of various complex spectroscopic data in a wide frequency range become significantly more efficient. However, the discretized WKT-FLT equation, obtained simply by replacing the integrations with the discrete summations, always produces two artifacts in the frequency-domain relaxation function. In addition, the artifacts become more apparent in the frequency-domain response function converted from the relaxation function. We find the sources of these artifacts that are associated with the discretization of the WKT-FLT equation. Taking these sources into account, we derive discretized WKT-FLT equations designated for both the frequency-domain relaxation and response functions with the artifacts removed. The use of the discretized WKT-FLT equations with the on-the-fly algorithm is illustrated by a flow chart. We also give application examples for the wave-vector-dependent dynamic susceptibility in an isotropic amorphous polyethylene and the frequency-domain response functions of the orientation vectors in an n-alkane crystal.

Influence of Ion Solvation on the Properties of Electrolyte Solutions.

It is widely appreciated that the addition of salts to water leads to significant changes in the thermodynamic and dynamic properties of these aqueous solutions that have great significance in biology and manufacturing applications. However, no theoretical framework currently exists that describes these property changes in an internally consistent fashion. In previous work, we developed a coarse-grained model of electrolyte solutions capable of reproducing basic trends on how salts influence the viscosity and water diffusion coefficient. The present work explores the predictions of this model for basic thermodynamic properties of electrolyte solutions, namely, the density, isothermal compressibility, and surface tension. On the basis of our model, we find that ion-specific effects on thermodynamics properties, and by extension the dynamics of electrolyte solutions, derive primarily from ion solvation.

Complex Coacervation in Polyelectrolytes from a Coarse-Grained Model.

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 of coacervation have been limited. In this work, a coarse-grained model of the polymers and the corresponding counterions is proposed and used to simulate coacervation as a function of polymer length and overall salt concentration. Several sampling methods are used to determine the phase behavior of the underlying polymers. In particular, the results of simulations in different ensembles are shown to be consistent and to reproduce a number of phenomena observed in experiments, including the disruption of complexation by increasing ionic strength or by decreasing molecular weight. The coacervate concentrations determined from phase behavior calculations are then used to examine the rheology of the corresponding materials. By relying on long dynamic simulations, we are able to generate the dynamic response of the material in the form of dynamic moduli as a function of frequency, which are also found to compare favorably with experimental measurements.

Coarse-Grained Model of the Dynamics of Electrolyte Solutions.

Ion-specific solvation has fundamental implications in biochemistry, and the thermodynamics and dynamics of aqueous salt solutions have correspondingly been investigated intensively. Nonetheless, there are fundamental unresolved issues in modeling the dynamics of aqueous salt solutions and the related problem of polymers dissolved in these solutions. In particular, experiments show that the self-diffusion coefficient, D, of water molecules in electrolyte solutions can be either enhanced or suppressed by particular salts having the same valence where the observed changes correlate with the Hofmeister series governing the relative solubility of proteins and water-soluble polymers in the same salt solutions. Recent studies have demonstrated that common atomistic models of aqueous electrolyte solutions completely fail to reproduce this basic phenomenon. Drawing on similar trends observed in the field of polymer nanocomposites, we propose a coarse-grained model of aqueous electrolyte solutions that captures the observed trends and that offers physical insight into the influence of salt on the thermodynamic and dynamic properties of electrolyte solutions.

Gel phase formation in dilute triblock copolyelectrolyte complexes.

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 in contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing concentration, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assembly of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously on solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chain aggregates in early stages of copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Our discoveries contribute to the fundamental understanding of the structure and pathways of complexation-driven assemblies, and raise intriguing prospects for gel formation at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.

A multi-chain polymer slip-spring model with fluctuating number of entanglements: Density fluctuations, confinement, and phase separation.

Coarse grained simulation approaches provide powerful tools for the prediction of the equilibrium properties of polymeric systems. Recent efforts have sought to develop coarse-graining strategies capable of predicting the non-equilibrium behavior of entangled polymeric materials. Slip-link and slip-spring models, in particular, have been shown to be capable of reproducing several key aspects of the linear response and rheology of polymer melts. In this work, we extend a previously proposed multi-chain slip-spring model in a way that correctly incorporates the effects of the fluctuating environment in which polymer segments are immersed. The model is used to obtain the equation of state associated with the slip-springs, and the results are compared to those of related numerical approaches and an approximate analytical expression. The model is also used to examine a polymer melt confined into a thin film, where an inhomogeneous distribution of polymer segments is observed, and the corresponding inhomogeneities associated with density fluctuations are reflected on the spatial slip-spring distribution.

A multichain polymer slip-spring model with fluctuating number of entanglements for linear and nonlinear rheology.

A theoretically informed entangled polymer simulation approach is presented for description of the linear and non-linear rheology of entangled polymer melts. The approach relies on a many-chain representation and introduces the topological effects that arise from the non-crossability of molecules through effective fluctuating interactions, mediated by slip-springs, between neighboring pairs of macromolecules. The total number of slip-springs is not preserved but, instead, it is controlled through a chemical potential that determines the average molecular weight between entanglements. The behavior of the model is discussed in the context of a recent theory for description of homogeneous materials, and its relevance is established by comparing its predictions to experimental linear and non-linear rheology data for a series of well-characterized linear polyisoprene melts. The results are shown to be in quantitative agreement with experiment and suggest that the proposed formalism may also be used to describe the dynamics of inhomogeneous systems, such as composites and copolymers. Importantly, the fundamental connection made here between our many-chain model and the well-established, thermodynamically consistent single-chain mean-field models provides a path to systematic coarse-graining for prediction of polymer rheology in structurally homogeneous and heterogeneous materials.

Entangled polymer dynamics in equilibrium and flow modeled through slip links.

The idea that the dynamics of concentrated, high-molecular weight polymers are largely governed by entanglements is now widely accepted and typically understood through the tube model. Here we review alternative approaches, slip-link models, that share some similarities to and offer some advantages over tube models. Although slip links were proposed at the same time as tubes, only recently have detailed, quantitative mathematical models arisen based on this picture. In this review, we focus on these models, with most discussion limited to mathematically well-defined objects that conform to state-of-the-art beyond-equilibrium thermodynamics. These models are connected to each other through successive coarse graining, using nonequilibrium thermodynamics along the way, and with a minimal parameter set. In particular, the most detailed level of description has four parameters, three of which can be determined directly from atomistic simulations. Once the remaining parameter is determined for any system, all parameters for all members of the hierarchy are determined. We show how, using this hierarchy of slip-link models combined with atomistic simulations, we can make predictions about the nonlinear rheology of monodisperse homopolymer melts, polydisperse melts, or blends of different architectures. Mathematical details are given elsewhere, so these are limited here, and physical ideas are emphasized. We conclude with an outlook on remaining challenges that might be tackled successfully using this approach, including complex flow fields and polymer blends.