Numerical study of a slip-link model for polymer melts and nanocomposites

We present a numerical study of the slip link model introduced by Likhtman for describing the dy- namics of dense polymer melts. After reviewing the technical aspects associated with the implemen- tation of the model, we extend previous work in several directions. The dependence of the relaxation modulus with the slip link density and the slip link stiffness is reported. Then the nonlinear rheolog- ical properties of the model, for a particular set of parameters, are explored. Finally, we introduce excluded volume interactions in a mean field such as manner in order to describe inhomogeneous systems, and we apply this description to a simple nanocomposite model. With this extension, the slip link model appears as a simple and generic model of a polymer melt, that can be used as an alternative to molecular dynamics for coarse grained simulations of complex polymeric systems

Electron tomography provides a direct link between the Payne effect and the inter-particle spacing of rubber composites.

Rubber-filler composites are a key component in the manufacture of tyres. The filler provides mechanical reinforcement and additional wear resistance to the rubber, but it in turn introduces non-linear mechanical behaviour to the material which most likely arises from interactions between the filler particles, mediated by the rubber matrix. While various studies have been made on the bulk mechanical properties and of the filler network structure (both imaging and by simulations), there presently does not exist any work directly linking filler particle spacing and mechanical properties. Here we show that using STEM tomography, aided by a machine learning image analysis procedure, to measure silica particle spacings provides a direct link between the inter-particle spacing and the reduction in shear modulus as a function of strain (the Payne effect), measured using dynamic mechanical analysis. Simulations of filler network formation using attractive, repulsive and non-interacting potentials were processed using the same method and compared with the experimental data, with the net result being that an attractive inter-particle potential is the most accurate way of modelling styrene-butadiene rubber-silica composite formation.L.S. and P.A.M thank Michelin for funding. The research leading to these results has received funding from the European Research Council under the European Union's Seventh Framework Programme (FP7/2007-2013)/ERC grant agreement 291522-3DIMAGE.This is the final published version. It first appeared at http://www.nature.com/srep/2014/141209/srep07389/full/srep07389.html

Depercolation of aggregates upon polymer grafting in simplified industrial nanocomposites studied with dielectric spectroscopy

The dynamics of polymer and filler in simplified industrial silica-styrene-butadiene nanocomposites (silica Zeosil 1165 MP, volume fraction 0-21%v) have been studied with broadband dielectric spectroscopy (BDS) and nuclear magnetic resonance (NMR). The fraction of graftable matrix chains was varied from 0 to 100%D3. The introduction of silica nanoparticles is shown to leave the segmental relaxation unaffected, an observation confirmed by the measurement of only a thin (some Angstroms thick) immobilized layer by NMR. The low-frequency measurements are resolved in two distinct dielectric Maxwell-Wagner-Sillars (MWS) processes of different behavior with respect to changes of large-scale silica structures induced by variations of filler fraction and grafting. It is found that increasing grafting leaves the first MWS-process unaffected, while it decreases the strength of the (slower) second MWS by about a decade. At constant silica volume fraction, this indicates depercolation of the filler, thereby providing a microscopic explanation of the evolution of rheological reinforcement. The sensitivity to large-scale reorganizations together with a characterization of local polymer dynamics provides insight over many length- and time-scales into structure and dynamics of nanocomposites, and thus the physical origin of the reinforcement effect.We are thankful for a “Chercheur d'Avenir” grant by the Languedoc-Roussillon region (J.O.) and Ph.D. funding “CIFRE” by Michelin (G.P.B.). The authors acknowledge financial support from the European Commission under the Seventh Framework Program by means of the grant agreement for the Integrated Infrastructure Initiative N. 262348 European Soft Matter Infrastructure (ESMI).Peer Reviewe

Interplay between Polymer Chain Conformation and Nanoparticles Assembly in Model Industrial Silica/Rubber Nanocomposites

International audienceThe question of the influence of nanoparticles (NP) on chain dimensions in polymer nanocomposites(PNC) has been treated mainly through the fundamental way using theoretical or simulation tools andexperiments on well-defined model PNC. Here we present the first experimental study about theinfluence of NP on the polymer chain conformation for PNC designed to be as close as possible toindustrial systems employed in tire industry. PNC are silica nanoparticles dispersed into a Styrene-Butadiene-Rubber (SBR) matrix whose NP dispersion can be managed by NP loading with interfacialcoating or coupling additives usually employed in the manufacturing mixing process. We associatedspecific chain (d) labeling, and the so-called Zero Average Contrast (ZAC) method, with SANS, in-situSANS and SAXS/TEM experiments to extract the polymer chain scattering signal at rest for non-crosslinked and under stretching for cross-linked PNCs. NP loading, individual clusters or connectednetwork, as well as the influence of the type, the quantity of interfacial agent and the influence of theelongation rate have been evaluated on the chain conformation and on its related deformation. Weclearly distinguish the situations where the silica is perfectly matched from the unperfected matching bydirect comparison of SANS and SAXS structure factor. Whatever the silica matching situation, theadditive type and quantity and the filler content, there is no thus significant change in the polymerdimension for NP loading up to 15% v/v within a range of 5%. One can see an extra scatteringcontribution at low Q, as often encountered, enhanced for non-perfect silica matching but also visiblefor perfect filler matching. This contribution can be qualitatively attributed to specific h or d chainsadsorption onto the NP surface inside the NP cluster that modifying the average scattering neutroncontrast of the silica cluster. Under elongation, NP act as additional cross-linking junction preventingchain relaxation giving a deformation of the chain with NP closer to theoretical phantom networkprediction than for pure matrix

Structure multiéchelles et propriétés des matériaux du pneu

Derrière l’aspect uniforme des matériaux du pneu, se dévoile à des échelles de quelques nanomètres un univers complexe. Une vision physico-chimique du procédé de fabrication des mélanges donne un éclairage sur la morphologie de répartitions aléatoires de petits objets fractals dans une matrice de polymère. On discute du lien entre les propriétés mécaniques mesurées au niveau macroscopique, la structure aux petites échelles des matériaux et le procédé d’obtention de cette structure. On illustre que le couplage entre expériences réelles et virtuelles via la simulation numérique est un atout fort de la démarche scientifique

A high-temperature dielectric process as a probe of large-scale silica filler structure in simplified industrial nanocomposites

The existence of two independent filler-dependent high-temperature Maxwell-Wagner-Sillars (MWS) dielectric processes is demonstrated and characterized in detail in silica-filled styrene-butadiene (SB) industrial nanocomposites of simplified composition using Broadband Dielectric Spectroscopy (BDS). The uncrosslinked samples are made with 140 kg mol-1 SB-chains, half of which carry a single graftable end-function (50% D3), and Zeosil 1165 MP silica incorporated by solid-phase mixing. While one high-temperature process is known to exist in other systems, the dielectric properties of a new silica-related process - strength, relaxation time, and activation energy - have been evidenced and described as a function of silica volume fraction and temperature. In particular, it is shown that its strength follows a percolation behavior as observed with the ionic conductivity and rheology. Moreover, activation energies show the role of polymer layers separating aggregates even when they are percolated. Apart from simultaneous characterization over a broad frequency range up to local polymer and silanol dynamics, it is believed that such high-temperature BDS-measurements can thus be used to detect reorganizations in structurally-complex silica nanocomposites. Moreover, they should contribute to a better identification of dynamical processes via the described sensitivity to structure in such systems.We are thankful for a ‘‘Chercheur d’Avenir’’ grant by the Languedoc-Roussillon region (J.O.) and PhD funding ‘‘CIFRE’’ by Michelin (G.P.B.). The authors acknowledge financial support from the European Commission under the Seventh Framework Program by means of the grant agreement for the Integrated Infrastructure Initiative No. 262348 European Soft Matter Infrastructure (ESMI).Peer Reviewe