Cellulosic nanoparticles with high Young's modulus, crystallinity, specific surface area, and aspect ratio can be found in the natural structure of plant fibers. Indeed, lignocellulosic fibers consist of semicrystalline cellulose nanofibrils embedded in an amorphous matrix mainly composed of lignin and hemicelluloses. These nanostructures give the mechanical strength to higher plant cells, and are biodegradable, renewable, resistant, and widely available to produce nanocomposites with low density, and improved and controlled mechanical, optical, and barrier properties. Nanoparticles can be extracted from cellulose using a top-down mechanically or chemically assisted deconstructing strategy, and owing to their highly reactive surface ensuing nanomaterials can be chemically modified to tailor their properties for a wide range of applications. This review is limited to cellulose chemically extracted nanocrystals and aims to provide an overview about several aspects that involve this material, including sources, properties, challenges, and perspectives.
The rheological properties of a dispersion of cellulose nanocry stals (CNC) in an aqueous sol ution of poly ox y ethy lene (PEO) hav e been inv estigated. A peculiar behav ior is reported. Upon adding CNC, the v iscosity of the suspension first decreases and then increases. Adsorption of PEO chains on the surface of the nanoparticles has been suspected. Freeze-dry ing of this PEO-adsorbed CNC dispersion was performed and the ensuing ly ophilisate was ex truded with low density poly ethy lene. Compared to neat CNC-based nanocomposites, both improv ed dispersibility and thermal stability were observ ed. This simple and phy s ical method constitutes an approach of choice for the melt processing of CNC-based nanocomposites with a hy drophobic poly meric matrix applicable at industrial scale.
The use of biodegradable polymers is of great importance nowadays in many applications. Some of the most commonly used biopolymers are polylactic acid (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) due to their superior properties and availability. In this manuscript, we use a facile and green modification method of organoclay (OC) by antimicrobial natural rosin which is considered as a toxicity-free reinforcing material, thus keeping the green character of the material. It increases the interlayer spacing between the clay platelets. This was proven by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) and found to impart antimicrobial properties to PLA/PBAT blends. The morphology of the resulting blends was conducted using scanning and transmission electron microscopies (SEM and TEM), and evidence of exfoliation and intercalation was observed. The thermal properties of the blends were studied using differential scanning calorimetry (DSC), and a detailed study of the crystallization of both PLA and PBAT was reported showing cold crystallization behavior of PLA. The final effect on mechanical and antimicrobial properties was also investigated. The obtained results reveal excellent possibility of using expanded OC modified PLA/PBAT polymer blends by adding a green material, antimicrobial natural rosin, for food packaging and biomembranes applications.
International audienceThe purpose of this study was to investigate a new way of processing cellulose whiskers reinforced polymer. A stable suspension of tunicin whiskers was obtained in an organic solvent (N,N-dimethylformamide) without a surfactant addition or a chemical surface modification. Both the high value of the dielectric constant of DMF and the medium wettability of tunicin whiskers were supposed to control the stability of the suspension. The nanocomposite materials were prepared by UV cross-linking using an unsaturated polyether as matrix. The resulting films were characterized by SEM, DSC, and mechanical testing in both the linear and nonlinear domains. The processing technique from a N,N-dimethylformamide suspension was found to be successful and led to materials whose properties are similar to those obtained with aqueous medium. It could be a good alternative to broaden the number of possible polymer matrices and to allow the processing of nanocomposite materials from an organic solvent solution instead of using aqueous suspensions
Polysaccharide nanocrystals with a rodlike shape but with different dimensions and specific surface area were prepared from cotton and capim dourado cellulose, and with a plateletlike morphology from waxy maize starch granules. The rheological behavior of aqueous solutions of poly(ethylene oxide) (PEO) with different molecular weights when adding these nanoparticles was investigated evidencing specific interactions between PEO chains and nanocrystals. Because PEO also bears hydrophobic moieties, it was employed as a compatibilizing agent for the melt processing of polymer nanocomposites. The freeze-dried mixtures were used to prepare nanocomposite materials with a low density polyethylene matrix by extrusion. The thermal and mechanical behavior of ensuing nanocomposites was studied.
International audienceThis paper deals with the performance of anhydrous proton-conducting polymers obtained by blending modified Nafion® membranes with proton conducting ionic liquids (PILs). It has been shown that the conductivities depend more on the PIL uptake than on its intrinsic conductivity. Conductivities at 130°C approaching those of current Nafion membranes at 80°C and 98% relative humidity were obtained with the best blends. These data allow considering MEA operating at 120-130°C based on membrane and electrodes incorporating these blends. This is clearly a positive feature for an implementation in hybrid vehicles powered by proton exchange membrane fuel cells (PEMFCs) operating above 100°C. Lastly, preliminary results for a PIL based on a half-neutralized diamine show an improvement in oxidation and, provided that the neutralization is optimized, a neat reinforcement of the Nafion membrane can be expected
On account to their high mechanical properties along with high reinforcing capacity, cellulose nanocrystals (CNCs) could be the ultimate choice for polymer nanocomposites as filler. Recently, different strategies have been investigated for the melt extrusion of CNC-based polymer nanocomposites because it is a solvent-free process and because this technique is more viable for commercial industrialization. However, most thermoplastic polymers are processed at high temperatures, and sulfuric acid preparation of CNC limits the processing because of surface sulfate groups degradation. In this study we profitably used these negatively charged groups, and quaternary ammonium salt was ionically adsorbed on CNC by a simple aqueous method. Fourier transform infrared spectroscopy, thermogravimetric analysis, and X-ray diffraction were used to characterize adsorbed CNC, and changes in polarity were investigated by contact angle measurements. Modified CNC was extruded with polypropylene at 190 °C, and the ensuing composites were characterized in terms of mechanical (by dynamic mechanical analysis and tensile tests), thermal (by differential scanning calorimetry), and morphological (scanning electron microscopy) properties. The melt rheology of PP-based nanocomposites was also reported.
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