A variety of materials were used to fabricate nanocoatings using layer-by-layer (LbL) assembly to reduce the flammability of cotton fabric. The most effective brominated flame retardants have raised concerns related to their toxicity and environmental impact, which has created a need for alternative flame retardant chemistries and approaches. Polymer nanocomposites typically exhibit reduced mass loss and heat release rates, along with anti-dripping behavior, all of which are believed to be due to the formation of a barrier surface layer. Despite these benefits, the viscosity and modulus of the final polymeric material is often altered, making industrial processing difficult. These challenges inspired the use of LbL assembly to create densely layered nanocomposites in an effort to produce more flame-retardant coatings. Laponite and montmorillonite (MMT) clay were paired with branched poly(ethylenimine) to create thin film assemblies that can be tailored by changing pH and concentration of aqueous deposition mixtures. Both films can be grown linearly as a function of layers deposited, and they contained at least 70 wt percent of clay. When applying these films to cotton fabric, the individual fibers are uniformly coated and the fabric has significant char left after burning. MMT-coated fabric exhibits reduced total heat release, suggesting a protective ceramic surface layer is created. Small molecule, POSS-based LbL thin films were also successfully deposited on cotton fabric. With less than 8 wt percent added to the total fabric weight, more than 12 wt percent char remained after microscale combustion calorimetry. Furthermore, afterglow time was reduced and the fabric weave structure and shape of the individual fibers were highly preserved following vertical flame testing. A silica-like sheath was formed after burning that protected the fibers. Finally, the first intumescent LbL assembly was deposited on cotton fabric. SEM images show significant bubble formation on fibers, coated with a 0.5 wt percent PAAm/1 wt percent PSP coating after burning. In several instances, a direct flame on the fabric was extinguished. The peak HRR and THR of coated fabric has 30 percent and 65 percent reduction, respectively, compared to the uncoated control fabric. These anti-flammable nanocoatings provide a relatively environmentally-friendly alternative for protecting fabrics, such as cotton, and lay the groundwork for rendering many other complex substrates (e.g., foam) flame-retardant without altering their processing and desirable mechanical behavior.

Actuellement, la stratégie de la production d’énergie repose sur les 3 concepts d’économie, de régénération et d’écologie. La production de biodiesel s’insère dans cette thématique et fait objet de ce travail. Un suivi cinétique de nucléation-croissance est réalisé sur des nanoparticules monodisperses d’oxo-alcoxydes de zirconium (ZOA). Ces nanoparticules sont préparées par voie sol-gel dans un réacteur à T-micro-mélangeur avec deux flux turbulents de ZNP et c dans 1-propanol à 20°C. Les nanodépôts des nanoparticules de ZOA ont été réalisés sur des substrats en silice et comparés aux nanopoudres récupérées après l’induction du sol de ZOA. Les nanodépôts et les poudres subissent un séchage à 80°C puis une imprégnation humide dans une solution aqueuse de 0,25 mol.L⁻¹ de H₂SO₄. Nous obtenons ainsi les nanodépôts catalytiques après une calcination à des températures comprises entre 500 et 700°C sous O₂. Les techniques de BET, ATG-ATD, MET, DRIFT, analyse élémentaire et DRX sont déployées pour caractériser ces catalyseurs. Les cinétiques du processus d’estérification et de transestérification ont été étudiées en fonction des conditions de la préparartion des catalyseurs nanostructurés. Les nanodépôts catalytiques acides de ZrO₂-SO₄²⁻ possèdent une activité catalytique 50 fois plus élevée que celle des nanopoudres dans la réaction d’estérification de l’acide palmitique dans le méthanol à 65°C. Les nanodépôts calcinés à 580°C ont la meilleure stabilité vis à vis des essais de recyclage. L’activité catalytique des nanodépôts est aussi valable avec d’autres charges dont la composition est similaire à celle des huiles non-comestibles puis celle des déchets gras. / In this work, we have realized novel nanoparticulate catalysts ZrO₂-SO₄²⁻ for biofuel production. We have studied nucleation-growth kinetics of zirconium-oxo-alkoxy (ZOA) nanoparticles in the sol-gel process. The monodispersed nanoparticles of 3.6 nm diameter were realised in a sol-gel reactor with rapid (turbulent) micro-mixing of liquid solutions containing ZNP and H₂O in 1-propanol at 20°C. The nanocoatings were realised of stable colloids of ZOA nanoparticles on silica beads along with common powders obtained after precipitation of unstable colloids. The acid ZrO₂-SO₄²⁻" catalysts were prepared after drying at 80°C, wet impregnation in 0.25 mol.L⁻¹ aqueous solution of sulfuric acid and subsequent thermal treatment between 500 and 700°C and studied with BET, DTA-DSC, TEM, DRIFT, elemental analysis, DRX and other methods. The catalyst nanocoatings calcinated at 580°C showed strong activity in esterification reaction of palmitic acid in methanol at 65°C, which is about 50 times higher than that of nanopowders, and also possesses the highest stability towards recycling. Tha catalytic performance of catalytic nanocoatings was also confirmed on unedible and waste oils.

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