Crosslinked Elastomers: Structure-Property Relationships and Stress-Optical Law.

We present a combination of independent techniques in order to characterize crosslinked elastomers. We combine well-established macroscopic methods, such as rheological and mechanical experiments and equilibrium swelling measurements, a more advanced technique such as proton multiple-quantum NMR, and a new method to measure stress-induced segmental orientation by in situ tensile X-ray scattering. All of these techniques give access to the response of the elastomer network in relation to the crosslinking of the systems. Based on entropic elasticity theory, all these quantities are related to segmental orientation effects through the so-called stress-optical law. By means of the combination of these techniques, we investigate a set of unfilled sulfur-vulcanized styrene butadiene rubber elastomers with different levels of crosslinking. We validate that the results of all methods correlate very well. The relevance of this approach is that it can be applied in any elastomer materials, including materials representative of various industrial application, without prerequisite as regards, e.g., optical transparency or simplified formulation. Moreover, the approach may be used to study reinforcement effects in filled elastomers with nanoparticles.

Efficient polynomial analysis of magic-angle spinning sidebands and application to order parameter determination in anisotropic samples.

Chemical shift tensors in 13C solid-state NMR provide valuable localized information on the chemical bonding environment in organic matter, and deviations from isotropic static-limit powder line shapes sensitively encode dynamic-averaging or orientation effects. Studies in 13C natural abundance require magic-angle spinning (MAS), where the analysis must thus focus on spinning sidebands. We propose an alternative fitting procedure for spinning sidebands based upon a polynomial expansion that is more efficient than the common numerical solution of the powder average. The approach plays out its advantages in the determination of CST (chemical-shift tensor) principal values from spinning-sideband intensities and order parameters in non-isotropic samples, which is here illustrated with the example of stretched glassy polycarbonate.

Competitive Adsorption between a Polymer and Solvents onto Silica.

In polymer nanocomposites, particle-polymer interactions play a key role both in the processing and in the final properties of the obtained materials. Specifically, for silica, because of the surface polarity, surface modification is commonly used to improve the compatibility with apolar polymer matrices in order to prevent agglomeration. In this work, a new way to investigate the polymer-silica affinity and determine dispersibility parameters (HDP) of silica particles in the 3D Hansen space using a solvent approach is proposed. These parameters are estimated from the assessment of the stability of suspensions in a set of organic solvents. Based on the respective locations of the solvent, polymer, and silica representative points in the 3D Hansen space, the adsorption of a given polymer in solution in a given solvent can be predicted. This is shown with the industrial precipitated silica Zeosil 1165MP in combination with polystyrene and polybutadiene. It is shown that silanization of the silica particles decreases the adsorption of polystyrene, even though because of this surface treatment, silica comes closer to polystyrene in the Hansen space. This counter-intuitive effect is rationalized based on the consideration of an adsorption parameter χS computed from the relative locations of the solvent, polymer, and particles in the 3D Hansen space. Basically, this parameter is related to the respective distances of the solvent and polymer representative points to that of the particle in the Hansen space.

Dielectric relaxation of thin films of polyamide random copolymers.

We investigate the relaxation behavior of thin films of a polyamide random copolymer, PA66/6I, with various film thicknesses using dielectric relaxation spectroscopy. Two dielectric signals are observed at high temperatures, the α process and the relaxation process due to electrode polarization (the EP process). The relaxation time of the EP process has a Vogel-Fulcher-Tammann type of temperature dependence, and the glass transition temperature, T(g), evaluated from the EP process agrees very well with the T(g) determined from the thermal measurements. The fragility index derived from the EP process increases with decreasing film thickness. The relaxation time and the dielectric relaxation strength of the EP process are described by a linear function of the film thickness d for large values of d, which can be regarded as experimental evidence for the validity of attributing the observed signal to the EP process. Furthermore, there is distinct deviation from this linear law for thicknesses smaller than a critical value. This deviation observed in thinner films is associated with an increase in the mobility and/or diffusion constant of the charge carriers responsible for the EP process. The α process is located in a higher-frequency region than the EP process at high temperatures but merges with the EP process at lower temperatures near the glass transition region. The thickness dependence of the relaxation time of the α process is different from that of the EP process. This suggests that there is decoupling between the segmental motion of the polymers and the translational motion of the charge carriers in confinement.

Nucleation and Growth of Ordered Copolymer Structures at Reactive Interfaces between PA6 and MA-g-HDPE.

We have studied the effect of the interfacial chemical reaction between PA6 and MA-g-HDPE in static conditions at a macroscopically flat interface. Interface destabilization and the growth of instabilities, somehow similar to myelin figures observed in surfactants put in the presence of water, are observed. For the first time in this system, it is shown that ordered microphase-separated copolymer domains, whose morphologies depend on the architecture of the copolymer, namely, essentially on the relative length of the blocks on each side of the interface, may nucleate and grow at a static interface between reactive polymers. We discuss the stability of the plane interface in the case of nonsymmetrical formed graft copolymers. The density of copolymers in the interface (coverage) can be estimated accurately from the long period of the formed structures. We confirm the predictions of Berezkin et al. This observation is very important since it confirms that nanometric domains are certainly generated during reactive extrusion, in addition to micrometric domains formed by rheological processes.

Constrained dynamics in interphases of model filled elastomers: role of interface chemistry on crosslinking, local stress distribution and mechanics.

The Franco-German consortium "DINaFil" (Dynamics at the Interface of Nanoscopic Fillers), located at Paris, Lyon and Halle, and co-funded by the ANR and the DFG, is a multidisciplinary endeavour concerned with a quantitative understanding of the complex behaviour of filled elastomers, a class of daily-life materials with as many uses as fundamentally open questions.