Improved Dual Network Model for Aging of Rubber Composites under Set Strains.

A new model is presented to predict rubber behavior during chemical aging at fixed strains. The model is validated using a carbon black-filled nitrile butadiene rubber aged in air at 125 °C. The model improves upon Tobolsky's dual network theory, designed for unfilled elastomers undergoing conventional aging but which has also often been used in rubber composites undergoing more complex aging scenarios. This work explores the shortcomings of the original model and demonstrates how the new model overcomes them. The model was validated using uniaxial tensile samples aged at 125 °C for 24-72 h at strains from 0-30%. The permanent set was measured, and the samples were tested on an Instron uniaxial test machine after aging. The cross-link density was estimated by equilibrium swelling. Results show that the new model more accurately models the stress-strain behavior to higher strains and provides more reliable estimates of chain scission and cross-linking after aging.

The Influence of Carbon Black Colloidal Properties on the Parameters of the Kraus Model.

The Payne Effect (also known as the Fletcher-Gent Effect) has a fundamental impact on the behavior of filled rubber composites and therefore must be considered during their design. This study investigates the influence of carbon black (CB) surface area and structure on the observed Payne Effect and builds on the existing models of Kraus and Ulmer to explain this phenomenon. Dynamic strain sweeps were carried out on natural rubber (NR) compounds containing eight different grades of CB at equivalent volume fractions. The loss and storage moduli were modeled according to the Kraus and Ulmer equations, using a curve optimization tool in SciPy. Subsequent regression analysis provided strong correlations between the fitting parameters and the CB structure and surface area. Using this regression analysis, this work provides further insight into the physical meaning behind the Kraus and Ulmer models, which are phenomenological in nature.

Design of functionalized biodegradable PHA-based electrospun scaffolds meant for tissue engineering applications.

Modification of electrospun nanofibrous poly(3-hydroxyalkanoate) (PHA)-based mats was implemented through two routes to obtain biomimetic scaffolds meant for tissue engineering applications. The first strategy relied on a physical functionalization of scaffolds thanks to an original route which combined both electrospinning and electrospraying, while the second approach implied the chemical modification of fiber surface via the introduction of reactive functional groups to further conjugate bioactive molecules. The degree of glycidyl methacrylate grafting on PHA reached 20% after 300s under photoactivation. Epoxy groups were modified via the attachment of a peptide sequence, such as Arg-Gly-Asp (RGD), to obtain biofunctionalized scaffolds. SEM and TEM analysis of mats showed uniform and well-oriented beadless fibers. The electrospinning/electrospraying tandem process afforded highly porous scaffolds characterized by a porosity ratio up to 83% and fibers with a surface largely covered by the electrosprayed bioceramic, i.e. hydroxyapatite. Gelatin was added to the latter PHA-based scaffolds to improve the hydrophilicity of the scaffolds (water contact angle about 0°) as well as their biological properties, in particular cell adhesion, proliferation, and osteogenic differentiation after 5days of human mesenchymal stromal culture. Human mesenchymal stromal cells exhibited a better adhesion and proliferation on the biofunctionalized scaffolds than that on non-functionalized PHA mats.

From design of bio-based biocomposite electrospun scaffolds to osteogenic differentiation of human mesenchymal stromal cells.

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.

Biocomposite scaffolds based on electrospun poly(3-hydroxybutyrate) nanofibers and electrosprayed hydroxyapatite nanoparticles for bone tissue engineering applications.

The electrospinning technique combined with the electrospraying process provides a straightforward and versatile approach for the fabrication of novel nanofibrous biocomposite scaffolds with structural, mechanical, and biological properties potentially suitable for bone tissue regeneration. In this comparative investigation, three types of poly(3-hydroxybutyrate) (PHB)-based scaffolds were engineered: (i) PHB mats by electrospinning of a PHB solution, (ii) mats of PHB/hydroxyapatite nanoparticle (nHA) blends by electrospinning of a mixed solution containing PHB and nHAs, and (iii) mats constituted of PHB nanofibers and nHAs by simultaneous electrospinning of a PHB solution and electrospraying of a nHA dispersion. Scaffolds based on PHB/nHA blends displayed improved mechanical properties compared to those of neat PHB mats, due to the incorporation of nHAs within the fibers. The electrospinning/electrospraying approach afforded biocomposite scaffolds with lower mechanical properties, due to their higher porosity, but they displayed slightly better biological properties. In the latter case, the bioceramic, i.e. nHAs, largely covered the fiber surface, thus allowing for a direct exposure to cells. The 21 day-monitoring through the use of MTS assays and SEM analyses demonstrated that human mesenchymal stromal cells (hMSCs) remained viable on PHB/nHA biocomposite scaffolds and proliferated continuously until reaching confluence.

Versatile photochemical surface modification of biopolyester microfibrous scaffolds with photogenerated silver nanoparticles for antibacterial activity.

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.

Photoinduced modification of the natural biopolymer poly(3-hydroxybutyrate-co-3-hydroxyvalerate) microfibrous surface with anthraquinone-derived dextran for biological applications.

A straightforward and versatile method for immobilizing polysaccharides on the surface of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBHV) electrospun fibers is developed with the objective of designing a new functional biomaterial having a significant effect on cell proliferation. The approach relies on a one-step procedure: UV grafting of a photosensitive dextran (AQ-Dext) on the surface of PHBHV fibers according to a "grafting onto" method, with the use of an anthraquinone derivative. The photografting is conducted through a photoinduced free radical process employing an anthraquinone-based photosensitizer in aqueous medium. Under appropriate conditions, AQ-Dext reacts with C-H σ-bonds of the polymer substrate (PHBHV) to produce a semianthraquinone radical according to an H-abstraction reaction. This radical recombines together with the alkylradical (R˙) formed at the surface of PHBHV fibers via the oxygen atom of the anthraquinone photolinker. The photochemical mechanism of the AQ-Dext photolysis is entirely described for the first time by an electron spin resonance technique and laser flash photolysis. The modified PHBHV microfibrous scaffolds are extensively characterized by water contact angle measurements, XPS analysis and atomic force microscopy, confirming the covalent grafting of dextran on PHBHV fibers. Finally, a primary investigation demonstrates that dextran modified PHBHV fibers are permissive for optimized cell colonization and proliferation. The cell morphologies are described by SEM micrographs, revealing a significant affinity and favorable interactions for adherence of human mesenchymal stem cells (hMSCs) on scaffolds provided by dextran chemical structure. Moreover, the proliferation rate of hMSCs increases on this new functionalized biomaterial associated with a higher extra-cellular matrix production after 5 days of culture in comparison with native PHBHV fibers.