Molecular Simulations of Controlled Polymer Crystallization in Polyethylene.

Multilamella polymer crystals are grown from the melt for the first time, in molecular dynamics simulations of a united-monomer model, with in excess of 1500000 united-monomers. Two-component systems comprised of equal weight fractions of 2000 united-monomer long chains and 200 united-monomer short chains are considered, with varying numbers of short butyl branches placed along the long chains. Utilizing two different cooling protocols, continuous-cooling and self-seeding, drastically different multilamella structures are revealed, which depend heavily on the branch content and crystallization protocol used. By self-seeding, well-aligned multilamella crystals are grown, which more clearly reveal the subtle alterations an increasing number of branches create on the size and shape of the crystallites in the early stages of spherulite formation. Under continuous cooling, this observation is almost completely obscured. At maximum thickness, chain portions as long as 100 united-monomers (200 carbons) are extended inside the crystalline lamella.

The memory of thin polymer films generated by spin coating.

We present results from isothermal and temperature-sweep creep experiments adapted to filaments which were derived from spin coated and subsequently crumpled thin polystyrene films. Due to the existence of residual stresses induced by preparation, the filaments showed significant shrinkage which we followed as a function of time at various temperatures. In addition, the influence of preparation conditions and subsequent annealing of supported thin polymer films on shrinkage and relaxation behavior was investigated. The temporal evolution of shrinkage revealed a sequence of relaxation regimes. We explored the temperature dependence of this relaxation and compared our observations with published results on drawn melt-spun fibers. This comparison revealed intriguing similarities between both systems prepared along different pathways. For instance, the magnitudes of shrinkage of melt-spun fibers and of filaments from crumpled spin coated polymer films are similar. Thus, our results suggest the existence of generic mechanisms of "forgetting", i.e., how non-equilibrated polymers lose their memory of past processing events.

Microscopic Structure of Compacted Polyelectrolyte Complexes: Insights from Molecular Dynamics Simulations.

We utilize atomistic molecular dynamics (MD) simulations to study local structural changes inside a polyelectrolyte complex consisting of poly(styrenesulfonate) (PSS) and poly(diallyldimethylammonium) (PDADMA) upon densification, in analogy to ultracentrifugation in experiments. In particular, we focus on the water content and on the reinforcement of the PSS-PDADMA network for various external accelerations. We demonstrate that apart from the formation of mesoscopic pores observed experimentally also the microscopic structure and the local relaxation processes likely affect the unique rheological properties of compacted polyelectrolyte complexes, as densification increases both the number of PSS-PDADMA coordinations and the intermixing of PSS and PDADMA. These processes slow down local rearrangements, thus further stabilizing the compacted state. We find that the concept of binary PSS-PDADMA salt bonds-relevant for theoretical models-is not strictly valid in the dense limit.

Diffusion of copolymers composed of monomers with drastically different friction factors in copolymer/homopolymer blends.

Copolymers are commonly used as interface modifiers that allow for the compatibilization of polymer components in a blend. For copolymers to function as a compatibilizer, they must diffuse through the matrix of the blend to the interface between the two blend components. The diffusivity of a copolymer in a blend matrix therefore becomes important in determining good candidates for use as compatibilizers. In this work, coarse-grained Monte Carlo simulations using the bond fluctuation model modified with an overlap penalty have been developed to study the diffusive behavior of PS/PMMA random copolymers in a PMMA homopolymer blend. The simulations vary the connectivity between different monomers, the thermodynamic interactions between the monomers which manifest within a chain, and between copolymer and homopolymer matrix and define the monomer friction coefficient of each component independently, allowing for the determination of the combined effect of these parameters on copolymer chain diffusion. The results of this work indicate that PS-r-PMMA copolymer diffusion is not linearly dependent on the copolymer composition on a logarithmic scale, but its diffusion is a balance of the kinetics governed by the dominant motion of the faster styrene monomers and thermodynamics, which are governed by the concentration of styrene monomer within a given monomer's local volume.

Semiflexible Chains at Surfaces: Worm-Like Chains and beyond.

We give an extended review of recent numerical and analytical studies on semiflexible chains near surfaces undertaken at Institut Charles Sadron (sometimes in collaboration) with a focus on static properties. The statistical physics of thin confined layers, strict two-dimensional (2D) layers and adsorption layers (both at equilibrium with the dilute bath and from irreversible chemisorption) are discussed for the well-known worm-like-chain (WLC) model. There is mounting evidence that biofilaments (except stable d-DNA) are not fully described by the WLC model. A number of augmented models, like the (super) helical WLC model, the polymorphic model of microtubules (MT) and a model with (strongly) nonlinear flexural elasticity are presented, and some aspects of their surface behavior are analyzed. In many cases, we use approaches different from those in our previous work, give additional results and try to adopt a more general point of view with the hope to shed some light on this complex field.

Disentanglement of Two Single Polymer Chains: Contacts and Knots.

Understanding the consequences of the noncrossing constraint is one of the remaining challenges in the physics of walks and polymers. To address this problem, we performed molecular simulations for the separation of only two initially connected, overlapping polymer chains with interactions tuned such that they are nearly random walks. The separation time for a configuration strongly correlates with the number of monomer contacts between both chains. We obtain a broad distribution of separation times with a slowly decaying tail. Knots only play a role for those configurations that contribute to the tail of the distribution. In contrast, when starting from the same initial configuration but allowing for chain crossings, separation is qualitatively faster and the time distribution narrow. The simulation results are rationalized by analytical theory. A theory of contacts based on polymer fractality and criticality is presented, along with the expected effects of knots.

New conserved structural fields for supercooled liquids.

By considering Voronoi tessellations of the configurations of a fluid, we propose two new conserved fields, which provide structural information not fully accounted for by the usual 2-point density correlation functions. One of these fields is scalar and associated with the volume of the Voronoi cell, whereas the other one, termed the "geometric polarisation", is vectorial and related to the local anisotropy of the configurations. We study the static and dynamical properties of these fields in the supercooled regime of a model glass-forming liquid. We show that the geometric polarisation is statically correlated to the force field, but contrary to it develops a plateau regime when the temperature is lowered. This different relaxation is related to the cage effect in glass-forming liquids, which prevents a complete relaxation of the shape of the cage around particle on intermediate time scales.

Mechanical behavior of linear amorphous polymers: comparison between molecular dynamics and finite-element simulations.

This paper studies the rheology of weakly entangled polymer melts and films in the glassy domain and near the rubbery domain using two different methods: molecular dynamics (MD) and finite element (FE) simulations. In a first step, the uniaxial mechanical behavior of a bulk polymer sample is studied by means of particle-based MD simulations. The results are in good agreement with experimental data, and mechanical properties may be computed from the simulations. This uniaxial mechanical behavior is then implemented in FE simulations using an elasto-viscoelasto-viscoplastic constitutive law in a continuum mechanics (CM) approach. In a second step, the mechanical response of a polymer film during an indentation test is modeled with the MD method and with the FE simulations using the same constitutive law. Good agreement is found between the MD and CM results. This work provides evidence in favor of using MD simulations to investigate the local physics of contact mechanics, since the volume elements studied are representative and thus contain enough information about the microstructure of the polymer model, while surface phenomena (adhesion and surface tension) are naturally included in the MD approach.

Structural properties of crystallizable polymer melts: Intrachain and interchain correlation functions.

We present results from constant pressure molecular-dynamics simulations for a bead-spring model of a crystallizable polymer melt. Our model has two main features, a chemically realistic intrachain rigidity and a purely repulsive interaction between nonbonded monomers. By means of intrachain and interchain structure factors we explore polymer conformation and melt structure above and below the temperature T{crys}{hom} of homogeneous crystallization. Here, we do not only determine average spatial correlations, but also site-specific correlations which depend on the position of the monomers along the polymer backbone. In the liquid phase above T{crys}{hom} we find that this site dependence can be well-accounted for by known theoretical approximations, the Koyama distribution for the intrachain structure and the polymer reference interaction site model (PRISM) for the interchain structure. This is no longer true in the semicrystalline phase. Below T{crys}{hom} short chains fully extend upon crystallization, whereas sufficiently long chains form chain-folded lamellae which coexist with amorphous regions. The structural features of these polymer crystals lead to violations of premises of the Koyama approximation or PRISM theory so that both theoretical approaches cannot be applied simultaneously. Furthermore, we find a violation of the Hansen-Verlet freezing criterion; our polymer melt crystallizes more easily than a simple liquid. This hints at the importance of the coupling between conformation (backbone rigidity) and density (packing constraints) for polymer crystallization.

Structural and conformational dynamics of supercooled polymer melts: insights from first-principles theory and simulations.

We report on quantitative comparisons between simulation results of a bead-spring model and mode-coupling theory calculations for the structural and conformational dynamics of a supercooled, unentangled polymer melt. We find semiquantitative agreement between simulation and theory, except for processes that occur on intermediate length scales between the compressibility plateau and the amorphous halo of the static structure factor. Our results suggest that the onset of slow relaxation in a glass-forming melt can be described in terms of monomer caging supplemented by chain connectivity. Furthermore, a unified atomistic description of glassy arrest and of conformational fluctuations that (asymptotically) follow the Rouse model emerges from our theory.

Static properties of a simulated supercooled polymer melt: structure factors, monomer distributions relative to the center of mass, and triple correlation functions.

We analyze structural and conformational properties in a simulated bead-spring model of a nonentangled, supercooled polymer melt. We explore the statics of the model via various structure factors, involving not only the monomers, but also the center of mass (CM). We find that the conformation of the chains and the CM-CM structure factor, which is well described by a recently proposed approximation [Europhys. Lett. 58, 53 (2002)]], remain essentially unchanged on cooling toward the critical glass transition temperature T(c) of mode-coupling theory. Spatial correlations between monomers on different chains, however, depend on temperature, albeit smoothly. This implies that the glassy behavior of our model cannot result from static intrachain or CM-CM correlations. It must be related to interchain correlations at the monomer level. Additionally, we study the dependence of interchain correlation functions on the position of the monomer along the chain backbone. We find that this site dependence can be well accounted for by a theory based on the polymer reference interaction site model. We also analyze triple correlations by means of the three-monomer structure factors for the melt and for the chains. These structure factors are compared with the convolution approximation that factorizes them into a product of two-monomer structure factors. For the chains this factorization works very well, indicating that chain connectivity does not introduce special triple correlations in our model. For the melt deviations are more pronounced, particularly at wave vectors close to the maximum of the static structure factor.