The nonlinear effect at small strains (Payne effect) has been investigated in the case of silica‐filled styrene‐butadiene rubber. The originality of this study lies in the careful preparation of samples in order to fix all parameters except one, that is, the modification of the silica surface by grafting silane (introduced at different concentrations) via reactive mixing. The organosilane can be either a coupling or a covering surface treatment with an octyl alkyl chain. A careful morphological investigation has been performed prior to mechanical characterization and silica dispersion was found to be the same whatever the type and the amount of silane. The increasing amount of covering agents was found to reduce the amplitude of the Payne effect. A similar decrease is observed for low coupling agent concentration. At higher concentrations, the evolution turns through an increase due to the contribution of the covalent bonds between the matrix and the silica acting as additional crosslinking. The discussion of the initial modulus was done in the frame of both the filler–filler and filler–polymer models. It is unfortunately not possible to distinguish both scenarios, because filler–filler and filler–matrix interactions are modified in the same manner by the grafting covering agent. On the other hand, the reversible decrease of the modulus versus strain (Payne effect) is interpreted in terms of debonding of the polymeric chains from the filler surface. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 286–298, 2007

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Electrospinning coupled with electrospraying provides a straightforward and robust route toward promising electrospun biocomposite scaffolds for bone tissue engineering. In this comparative investigation, four types of poly(3-hydroxybutyrate) (PHB)-based nanofibrous scaffolds were produced by electrospinning a PHB solution, a PHB/gelatin (GEL) mixture or a PHB/GEL/nHAs (hydroxyapatite nanoparticles) mixed solution, and by electrospinning a PHB/GEL solution and electrospraying a nHA dispersion simultaneously. SEM and TEM analyses demonstrated that the electrospun nHA-blended framework contained a majority of nHAs trapped within the constitutive fibers, whereas the electrospinning-electrospraying combination afforded fibers with a rough surface largely covered by the bioceramic. Structural and morphological characterizations were completed by FTIR, mercury intrusion porosimetry, and contact angle measurements. Furthermore, an in vitro investigation of human mesenchymal stromal cell (hMSC) adhesion and proliferation properties showed a faster cell development on gelatin-containing scaffolds. More interestingly, a long-term investigation of hMSC osteoblastic differentiation over 21 days indicate that hMSCs seeded onto the nHA-sprayed scaffold developed a significantly higher level of alkaline phosphatase activity, as well as a higher matrix biomineralization rate through the staining of the generated calcium deposits: the fiber surface deposition of nHAs by electrospraying enabled their direct exposure to hMSCs for an efficient transmission of the bioceramic osteoinductive and osteoconductive properties, producing a suitable biocomposite scaffold for bone tissue regeneration.

The effect of different silica treatments on the vulcanization of silica filled Styrene Butadiene Rubber (SBR) is investigated. The concentration, the length and the functionality (coupling or non coupling) of the silane used for this treatment are the parameters studied. It is shown that the silane grafting, by covering the silica surface, modifies the adsorption and desorption on this surface of the accelerators used in the vulcanization system, which in turn modifies the crosslinking kinetic and therefore should influence the final crosslinking state of the matrix.

International audienceOriginal in situ measurements of volume variation and small angle light scattering (SALS) are performed on silica filled Styrene Butadiene Rubber (SBR) during tensile tests. The influence of the silica treatment on the mechanisms involved is explored with sample carefully characterised and with the same filler dispersion. Two different types of silane are used as treatment, an alkoxy silane (so called covering agent) and a coupling agent which enables covalent bonds between the silica and the polymer matrix. It is shown that the coupling agent delays void formation in the samples and leads at intermediary strain to the reorganisation of the filler structure while the covering agent eases the void formation which also occurs without silica surface treatment

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A straightforward and versatile method for immobilizing macromolecules and silver nanoparticles on the surface of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBHV) electrospun fibers is developed with the objective of designing a new functional material having significant antibacterial activity. The approach relies on a two-step procedure: UV photografting of poly(methacrylic acid) (PMAA) on the surface of PHBHV fibers according to a "grafting from" method, and complexation of in situ photogenerated silver nanoparticles (Ag NPs) by carboxyl groups from tethered PMAA chains. The photografting process is conducted through a photoinduced free-radical process employing a ketone-based photoinitiator in aqueous medium. Under appropriate conditions, the photogenerated radicals abstract hydrogen atoms from the PHBHV backbone, thus initiating the UV-mediated photopolymerization of MAA from the PHBHV microfibrous surface. The photochemical mechanism of the ketone photolysis is entirely described by the electron spin resonance/spin-trapping technique, and the modified PHBHV microfibrous scaffold is extensively characterized by ATR-FTIR spectroscopy, water contact-angle measurements, and mercury intrusion porosimetry. In a second step, the in situ synthesis of Ag NPs within the microfibrous scaffold is implemented by photoreduction reaction in the presence of both a silver precursor and a photosensitizer. The photoinduced formation of Ag NPs is confirmed by UV spectrophotometry and XPS analysis. SEM and TEM experiments confirm the formation and dispersion of Ag NPs on the surface of the modified fibers. Finally, a primary investigation is conducted to support the antibacterial activity of the new functionalized biomaterial against Staphylococcus aureus and Escherichia coli.

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