Coarse-Grained Lattice Modeling and Monte Carlo Simulations of Stress Relaxation in Strain-Induced Crystallization of Rubbers.

Two-dimensional triangulated surface models for membranes and their three-dimensional (3D) extensions are proposed and studied to understand the strain-induced crystallization (SIC) of rubbers. It is well known that SIC is an origin of stress relaxation, which appears as a plateau in the intermediate strain region of stress-strain curves. However, this SIC is very hard to implement in models because SIC is directly connected to a solid state, which is mechanically very different from the amorphous state. In this paper, we show that the crystalline state can be quite simply implemented in the Gaussian elastic bond model, which is a straightforward extension of the Gaussian chain model for polymers, by replacing bonds with rigid bodies or eliminating bonds. We find that the results of Monte Carlo simulations for stress-strain curves are in good agreement with the reported experimental data of large strains of up to 1200%. This approach allows us to intuitively understand the stress relaxation caused by SIC.

Energy conversion in magneto-rheological elastomers.

Magneto-rheological (MR) elastomers contain micro-/nano-sized ferromagnetic particles dispersed in a soft elastomer matrix, and their rheological properties (storage and loss moduli) exhibit a significant dependence on the application of a magnetic field (namely MR effect). Conversely, it is reported in this work that this multiphysics coupling is associated with an inverse effect (i.e. the dependence of the magnetic properties on mechanical strain), denoted as the pseudo-Villari effect. MR elastomers based on soft and hard silicone rubber matrices and carbonyl iron particles were fabricated and characterized. The pseudo-Villari effect was experimentally quantified: a shear strain of 50 % induces magnetic induction field variations up to 10 mT on anisotropic MR elastomer samples, when placed in a 0.2 T applied field, which might theoretically lead to potential energy conversion density in the mJ cm-3 order of magnitude. In case of anisotropic MR elastomers, the absolute variation of stiffness as a function of applied magnetic field is rather independent of matrix properties. Similarly, the pseudo-Villari effect is found to be independent to the stiffness, thus broadening the adaptability of the materials to sensing and energy harvesting target applications. The potential of the pseudo-Villari effect for energy harvesting applications is finally briefly discussed.

Latex imaging by environmental STEM: application to the study of the surfactant outcome in hybrid alkyd/acrylate systems.

Among other uses, latexes are a successful alternative to solvent-borne binders for coatings. Efforts are made to produce hybrid nanostructured latexes containing an acrylic phase and an alkyd phase. However, after the film-forming process, the surfactant used to stabilize these latexes remains in the film, and its location can have a drastic effect on the application properties. Among the processing parameters, the alkyd hydrophobicity can strongly influence this location. This article aims at the imaging of these surfactant molecules in two hybrid latexes with different hydrophobicity level of the alkyd resin. A first part of this paper is dedicated to the understanding of the contrast provided by the surfactant in environmental STEM imaging of latexes. Then, the influence of surfactant-polymer affinity on the surfactant location after film-forming of those hybrid alkyd/acrylate latexes is studied by this technique. It is shown that in the hybrid latex with an alkyd shell (obtained with the most hydrophilic resin), the surfactant molecules tend to remain buried in the alkyd phase. Conversely, in the hybrid latex with an acrylate shell (in the case of the most hydrophobic resin), the surfactant molecules tend to gather into islands like in pure acrylate latex films.

Grafting of polystyrene on nitrogen-doped multi-walled carbon nanotubes.

Polymer grafting of polystyrene (PS) on nitrogen-doped multiwall carbon nanotubes (CNx) was successfully obtained by a "grafting from" technique. The production method involves the immobilization of initiators, using wet chemistry, onto the nanotube surface, followed by an in situ surface-initiated polymerization. The polymer-grafting carbon nanotubes synthesis includes the free radical functionalization of CNx and the "controlled/living" Nitroxide Mediated Radical Polymerization (NMRP). The obtained products were studied using several microscopic techniques as scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and electron energy loss spectroscopy (EELS). The characterization also includes thermogravimetric analysis (TGA), Raman spectroscopy, infrared spectroscopy, and electron spin resonance (ESR), among others. The analyzed samples were also compared with solutions fabricated by physical blending of the polymer and CNx nanotubes. These results indicate that the nanotube radical functionalization, the chemical grafting, and the polymerization reaction were obtained over CNx when NMRP method was successfully used, giving rise to a uniform PS layer of several nanometers grafted on the outer surface of the CNx nanotubes. Several properties of the PS-grafted CNx nanotubes were also studied. It is shown that the production method leads to a narrower distribution of the external diameters. Moreover, their solubilization in organic solvents is greatly improved. Finally, the dispersion of PS-grafted CNx into a PS matrix is studied to determine the differences in filler dispersion and interfacial adhesion strength, in comparison with nanocomposites elaborated with as-produced CNx.