High-pressure Brillouin [1] and polarized Raman spectra [2] of vitreous silica are measured up to 8 GPa in diamond-anvil cell at room temperature. On one hand, Brillouin frequencies show that the well-known anomalous maximum in the pressure dependence of the compressibility is suppressed by He incorporation into the silica network. This shows that the elastic anomaly relates to the collapse of the largest interstitial voids in the structure. On the other hand, the combined use of either a nonpenetrating pressurizing medium-argon-or a penetrating one-helium and Neon, allows one to separate density from stress effects on the Raman frequencies.[1]C. Weigel, A. Polian, M. Kint, B. Ruffl ́e, M. Foret, and R. Vacher, Phys. Rev. Lett. 109, 245504 , 2012[2]C. Weigel, M. Foret, B. Hehlen, M. Kint, S. Cl ́ement, A. Polian, R. Vacher, and B. Ruffl ́e, Phys. Rev. B 93, 224303 , 2016

Despite an abundant literature on epoxy-amine systems, a complete description of the curing kinetics in epoxy-phenol composites was still lacking. In this study, the curing kinetics of an epoxy-phenol composite relevant to microelectronics industry is probed by isothermal and non-isothermal differential scanning calorimetry. An isoconversional analysis of the data reveals a significant contribution of the diffusion of molecular species to the activation energy, at low temperature and high degrees of curing. A model-fitting of the kinetics is performed in two successive steps: high-temperatures data are fitted with Arrhenius law and nth order autocatalytic model (where the diffusion contribution is neglected), whereas low-temperature data are fitted using Rabinowitch and modified-Williams-Landel-Ferry models (considering a diffusion contribution related to the glass transition). The chemical and diffusion contributions to the rate constants are calculated at various temperatures, clarifying the kinetics regimes with precision. Finally, the kinetics regimes are summarized in an improved time-temperature-transformation diagram.

Polymer nanocomposites (PNCs) are made by dispersion of hard fillers in a polymer matrix, where the fillers are usually added to enhance mechanical properties. Thus, such materials attract industrial interest and their investigation is essential for the improvement of their performances.The present study concerns nanocomposites obtained using hydrophilic silica nanoparticles (NPs) dispersed in a soft polymer matrix of styrene-butadiene, commonly used in car tire manufacturing. The mechanical performances of such PNCs are strongly related to the structural properties: the dispersion state of silica particles in the polymer melt is governed by the mixing protocols (e.g., solid phase mixing or solvent casting) and thermodynamics of the system (i.e., particle miscibility) which influence the filler-filler and the filler-polymer interactions.We developed a new model nanocomposite system, equivalent to a simplified industrial one, made by solvent casting technique using colloidal silica NPs. In such model PNCs, the dispersion of colloidal silica is tuned via the surface-modification of silica particles by grafting hydrophobic molecules, i.e., silane coating agents, which promote the filler-polymer compatibility.To describe NP structure in solvents and after casting into polymer matrix, we propose a new method which combines Small Angle X-ray Scattering (SAXS), reverse Monte Carlo (RMC) and aggregate recognition (AR) analysis. This approach allows obtaining a detailed structural characterization of the silica NPs surface-modified with different silane grafting groups (i.e., tri-ethoxy, tri-methoxy or mono-methoxy silane). In particular, we show that silane molecules with trifunctional grafting functions may lead to the formation of polycondensed patches (i.e., reaction of lateral groups with neighboring molecules) on silica surface, favoring attractive interactions. Thus, the lowest aggregation is observed using mono-functionalized silane molecules where patches cannot form.Next, the SAXS-RMC-AR approach will be extended to investigate the structural properties of nanocomposite systems where silica NPs are surface-modified with silane molecules of various alkyl chain.

Tuning local nanoparticle arrangements and dynamical properties in polymer nanocomposites by grafting of small molecules

Upon mechanical loading, granular materials yield and undergo plastic deformation. The nature of plastic deformation is essential for the development of the macroscopic constitutive models and the understanding of shear band formation. However, we still do not fully understand the microscopic nature of plastic deformation in disordered granular materials. Here we used synchrotron X-ray tomography technique to track the structural evolutions of three-dimensional granular materials under shear. We establish that highly distorted coplanar tetrahedra are the structural defects responsible for microscopic plasticity in disordered granular packings. The elementary plastic events occur through flip events which correspond to a neighbor switching process among these coplanar tetrahedra (or equivalently as the rotation motion of 4-ring disclinations). These events are discrete in space and possess specific orientations with the principal stress direction.