Cinnamic acid and acetosyringone recrystallize in vegetable oil as platelets and rods respectively. After dissolution at high temperature(100°C) and upon cooling down to room temperature, their crystallites aggregate into a tenuous network which spans the entire volume of the system even at low mass fraction such as 1%. The whole system behaves as a soft solid characterized by an elastic modulus reaching 1MPa for mass fraction below 10% in the linear regime. The elastic modulus of cinnamic acid based oleogels varies with mass fraction as (-0) 2. For acetosyringone based oleogels, the elastic modulus varies non monotonically with concentration. This has been correlated to a morphological crossover from jammed spherulites at low mass fraction to entangled rods at higher mass fraction. Spherulite formation is related to the presence of branching points along the rods that result from secondary nucleation events. A new empirical parameter is defined from rheological data which reflects how far from equilibrium the solidification proceeds in nonisothermal conditions. This parameter accounts for the different concentration regimes of morphology and rheological properties that have been observed experimentally for acetosyringone.

The antagonistic effect of processing and thermal annealing on both the filler structure and the polymer matrix is explored in polymer nanocomposites based on natural rubber with precipitated silica incorporated by coagulation from aqueous suspension followed by roll-milling. Their structure and linear and non-linear rheology have been studied, with a particular emphasis on the effect of high temperature thermal treatment and the number of milling passes. Small-angle X-ray scattering intensities show that the silica is organized in small, unbreakable aggregates containing ca. 50 primary nanoparticles, which are reorganized on a larger scale in filler networks percolating at the highest silica contents. As expected, the filler network structure is found to be sensitive to milling, more milling inducing rupture, as evidenced by the decreasing Payne effect. After thermal treatment, the nanocomposite structure is found to be rejuvenated, erasing the effect of the previous milling on the low-strain modulus. In parallel, the dynamics of the samples described by the rheology or the calorimetric glass-transition temperature remain unchanged, whereas the natural latex polymer network structure is modified by milling towards a more fluid-like rheology, and cannot be recovered.

We investigate the linear viscoelasticity of polymer gels produced by the dispersion of gluten proteins in water:ethanol binary mixtures with various ethanol contents, from pure water to 60% v/v ethanol. We show that the complex viscoelasticity of the gels exhibits a time/solvent composition superposition principle, demonstrating the self-similarity of the gels produced in different binary solvents. All gels can be regarded as near critical gels with characteristic rheological parameters, elastic plateau and characteristic relaxation time, which are related one to another, as a consequence of self-similarity, and span several orders of magnitude when changing the solvent composition. Thanks to calorimetry and neutron scattering experiments, we evidencea co-solvency effect with a better solvation of the complex polymer-like chains of the gluten proteins as the amount of ethanol increases. Overall the gel viscoelasticity can be accounted for by a unique characteristic length characterizing the crosslink density of the supramolecular network, which is solvent composition-dependent. On a molecular level, these findings could be interpreted as a transition of the supramolecular interactions, mainly H-bonds, from intra- to interchains, which would be facilitated by the disruption of hydrophobic interactions by ethanol molecules. This work provides new insight for tailoring the gelation process of complex polymer gels.

In this article, we review both theoretical models and experimental results on the motion of micro-and nano-particles that are close to a fluid interface or move in between two fluids. Viscous drags together with dissipations due to fluctuations of the fluid interface and its physicochemical properties affect strongly the translational and rotational drags of colloidal particles, which are subjected to Brownian motion in thermal equilibrium. Even if many theoretical and experimental investigations have been carried out, additional scientific efforts in hydrodynamics, statistical physics, wetting and colloid science are still needed to explain unexpected experimental results and to measure particle motion in time and space scales, which are not accessible so far.

Industrial and model polymer nanocomposites are often formulated with coating agents to improve polymer-nanoparticle (NP) compatibility. Here the localization of silane coating agents in styrene-butadiene nanocomposite is investigated through the segmental dynamics of the polymer matrix by broadband dielectric spectroscopy (BDS), allowing the detection of silanes in the matrix through their plasticization effect. This acceleration of dynamics was followed via the shift of τmax of the α-relaxation induced by the presence of coating agents of different molecular weight and quantity, for different amounts of incorporated colloidal silica NPs (R ≈ 12.5 nm, polydispersity 12%). Any noteworthy contribution of interfacial polymer layers on τmax has been excluded by reference measurements with bare NPs. Our approach allowed quantifying the partition between the matrix and the NP interfaces, and was confirmed independently by calorimetry. As a control parameter, the silane grafting reaction could be activated or not, which was confirmed by the absence (resp. presence) of partitioning with the matrix. Our main result is that in the first steps of material formulation, before any grafting reaction, coating agents both cover the silica surface by adsorption and mix with the polymer matrix-in particular if the latter has chemical compatibility via its functional groups. Silane adsorption was found to be comparable to the grafted amount (1.1 nm-2), and does not increase further, confirming that the plateau of the adsorption isotherm is reached in industrial formulations. These results are hoped to contribute to a better understanding of the surface reactions taking place during complex formulation processes of nanocomposites, namely the exact amounts at stake, e.g., in industrial mixers. Final material properties are affected both through NP-matrix compatibility and plasticization of the latter by unreacted molecules. 2

Large deformations of soft elastic beads spinning at high angular velocity in a denser background fluid are investigated theoretically, numerically, and experimentally using millimeter-size polyacry-lamide hydrogel particles introduced in a spinning drop tensiometer. We determine the equilibrium shapes of the beads from the competition between the centrifugal force and the restoring elastic and surface forces. Considering the beads as neo-Hookean up to large deformations, we show that their elastic modulus and surface energy constant can be simultaneously deduced from their equilibrium shape. Also, our results provide further support to the scenario in which surface energy and surface tension coincide for amorphous polymer gels.

Numerical simulations of a drop crossing a plane liquid-liquid interface in a centrifugal field have been performed by using the Level-Set method. The objective is to characterize the hydrodynamical parameters controlling the coating volume of the droplet, which results from the rupture of the liquid column of lighter phase entrained by the droplet during the crossing of the interface in the tailing regime. The numerical method has been first validated in two-phase flow simulations of a drop rising in a stagnant liquid, then in three-phase flow configurations to reproduce the theoretical critical condition for a drop to cross an interface in static conditions (without initial velocity). Then, in inertial conditions, extensive simulations of crossing droplets have been performed in a wide range of flow parameters and phase properties, for two types of drop: solid-like droplets (mimicking rigid particles) and deformable drops. The crossing criteria is found to remain very close to that given by the theory in static conditions, either for a spherical or a deformed droplet. For each studied case, the crossing time, the maximum length of the column of liquid pulled by the droplet and the volume encapsulating the drop after crossing have been computed and scaled as a function of an inertia parameter, which is the ratio F* between the inertial stresses pushing on the interface, defined from the minimum drop velocity reached during crossing as characteristic velocity, and the opposite stress pulling back the entrained column towards the interface. The maximal column length increases with F* (when rescaled by the minimal inertial required for crossing) under two distinct growth rates according to the flow regime in the column. For solid-like drops, the final coating volume is a unique function of F*, and grows with F* at large inertia. In the case of deformable droplets, the coating volume evolution can also be well predicted by F* but corrected by the drop-to-film viscosity ratio, which strongly affects the drainage rate of the film along the drop surface during the encapsulation process.