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.

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.

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.

Self-assembling peptides (SAPs) have been extensively studied for their ability to form nanoscale ordered structures driven by noncovalent molecular interactions. Meanwhile, polymerization-induced self-assembly (PISA) has been exploited as a facile and efficient way to produce various amphiphilic block copolymer nano-objects, whose self-assembly was governed predominantly by the interactions of the different blocks with the polymerization medium. In this work, we combined PISA with SAPs to prepare novel peptide–polymer hybrid nano-objects, thus harnessing the advantages of PISA and the self-assembling driving force of SAPs. A tripeptide methacrylamide derivative (MAm-Gly-Phe-Phe-NH2, denoted as MAm-GFF, where MAm means methacrylamide) was copolymerized with glycerol monomethacrylate (GMA) to produce a P(GMA65-stat-(MAm-GFF)7) macro-chain transfer agent (macro-CTA) by reversible addition–fragmentation chain transfer polymerization in dimethylformamide. This peptide-based macro-CTA was then successfully chain-extended with poly(2-hydroxypropyl methacrylate) (PHPMA) by aqueous dispersion PISA, forming P(GMA65-stat-(MAm-GFF)7)-b-PHPMA28 self-assembled objects. Fibrous structures were observed by transmission electron microscopy (TEM) and Cryo-TEM, in agreement with depolarized dynamic light scattering, static light scattering, and small-angle X-ray scattering experiments that also revealed long anisotropic morphologies. Such structures have not been reported previously for PISA-prepared nano-objects. This confirms the decisive influence of the GFF SAP on the self-assembly. In addition, annealing the PISA suspension at different temperatures led to a significant size decrease in the self-assembled objects and to a morphological transition caused by the thermosensitivity of both the core-forming PHPMA block and the stabilizing P(GMA-stat-(MAm-GFF)) block.

We investigate freely expanding liquid sheets made of either simple Newtonian fluids or solutions of high molecular water-soluble polymer chains. A sheet is produced by the impact of a drop on a quartz plate covered with a thin layer of liquid nitrogen that suppresses shear viscous dissipation thanks to an inverse Leidenfrost effect. The sheet expands radially until reaching a maximum diameter and subsequently recedes. Experiments indicate the presence of two expansion regimes: the capillary regime, where the maximum expansion is controlled by surface tension forces and does not depend on the viscosity, and the viscous regime, where the expansion is reduced with increasing viscosity. In the viscous regime, the sheet expansion for polymeric samples is strongly enhanced as compared to that of Newtonian samples with comparable zero-shear viscosity. We show that data for Newtonian and non-Newtonian fluids collapse on a unique master curve where the maximum expansion factor is plotted against the relevant effective \textit{biaxial extensional} Ohnesorge number that depends on fluid density, surface tension and the biaxial extensional viscosity. For Newtonian fluids, this biaxial extensional viscosity is six times the shear viscosity. By contrast, for the non-Newtonian fluids, a characteristic \textit{Weissenberg number}-dependent biaxial extensional viscosity is identified, which is in quantitative agreement with experimental and theoretical results reported in the literature for biaxial extensional flows of polymeric liquids.

We analyze stress distributions in a two-dimensional bidisperse cemented granular packing for a broad range of the values of particle-size ratio, the volumes of large and small particles, and the amount of cementing matrix. In such textured porous materials, the stress concentration, which controls the fracture and fragmentation of the material under tensile loading or in grinding processes, reflects not only the porosity but also the contact network of the particle phase and the resulting stress chains. By means of peridynamic simulations under tensile loading, we show how both the texture and stress distribution depend on size ratio, volume ratio, and the amount of the cementing matrix. In particular, the volume fraction of the class of small particles plays a key role in homogenizing stresses across the system by reducing porosity. Interestingly, the texture controls not only the porosity but also the distribution of pores inside the system with its statistical variability, found to be strongly correlated with the homogeneity of stresses inside the large particles. The most homogeneous stress distribution occurs for the largest size ratio and largest volume fraction of small particles, corresponding to the lowest pore size dispersion and the cushioning effect of small particles and its similar role to the binding matrix for stress redistribution across the packing. At higher porosity, the tensile stresses above the mean stress fall off exponentially in all phases with an exponent that strongly depends on the texture. The exponential part broadens with decreasing matrix volume fraction and particle-size ratio. These correlations reveal the strong interplay between size polydispersity and the cohesive action of the binding matrix for stress distribution, which is significant for the behavior of textured materials in grinding operations.