Hybrid Films from Blends of Castor Oil and Polycaprolactone Waterborne Polyurethanes.

Waterborne polyurethanes (WBPUs) with relatively high biobased content (up to 43.7%) were synthesized, aiming at their use as coatings for metals and woods. The study was performed on self-standing films obtained from anionic polyurethane water dispersions (PUDs). The initially targeted PUD was prepared from castor oil (CO), while tartaric acid (TA), a byproduct of wine production, was utilized as the internal anionic emulsifier. Although the films were cohesive and transparent, they were fragile, and thus blending the CO-TA PUD with other WBPUs was the chosen strategy to obtain films with improved handling characteristics. Two different WBPUs based on polycaprolactone diol (PCL), a biodegradable macrodiol, were prepared with dimethylolpropionic acid (DMPA) and tartaric acid (TA) as synthetic and biobased internal emulsifiers, respectively. The use of blends with PCL-TA and PCL-DMPA allowed for tailoring the moduli of the samples and also varying their transparency and haze. The characterization of the neat and hybrid films was performed by colorimetry, FTIR-ATR, XRD, DMA, TGA, solubility and swelling in toluene, and water contact angle. In general, the addition of PCL-based films increases haze; reduces the storage modulus, G', which at room temperature can vary in the range of 100 to 350 MPa; and reduces thermal degradation at high temperatures. The results are related to the high gel content of the CO-TA film (93.5 wt.%), which contributes to the cohesion of the blend films and to the crystallization of the PCL segments in the samples. The highest crystallinity values corresponded to the neat PCL-based films (32.3% and 26.9%, for PCL-DMPA and PCL-TA, respectively). The strategy of mixing dispersions is simpler than preparing a new synthesis for each new requirement and opens possibilities for new alternatives in the future.

Nanocelluloses Reinforced Bio-Waterborne Polyurethane.

The aim of this work was to evaluate the influence of two kinds of bio- nano-reinforcements, cellulose nanocrystals (CNCs) and bacterial cellulose (BC), on the properties of castor oil-based waterborne polyurethane (WBPU) films. CNCs were obtained by the acidolysis of microcrystalline cellulose, while BC was produced from Komagataeibacter medellinensis. A WBPU/BC composite was prepared by the impregnation of a wet BC membrane and further drying, while the WBPU/CNC composite was obtained by casting. The nanoreinforcement was adequately dispersed in the polymer using any of the preparation methods, obtaining optically transparent compounds. Thermal gravimetric analysis, Fourier-transform infrared spectroscopy, field emission scanning electron microscopy, dynamical mechanical analysis, differential scanning calorimetry, contact angle, and water absorption tests were carried out to analyze the chemical, physical, and thermal properties, as well as the morphology of nanocelluloses and composites. The incorporation of nanoreinforcements into the formulation increased the storage modulus above the glass transition temperature of the polymer. The thermal stability of the BC-reinforced composites was slightly higher than that of the CNC composites. In addition, BC allowed maintaining the structural integrity of the composites films, when they were immersed in water. The results were related to the relatively high thermal stability and the particular three-dimensional interconnected reticular morphology of BC.

Cellulose nanocrystals suspensions: Liquid crystal anisotropy, rheology and films iridescence.

The properties of aqueous suspensions of cellulose nanocrystals (CNC) and their casted films are revised. The bio-nanoparticles are briefly introduced, including modifications of the crystals and the suspending media. The formation of CNC-derived liquid crystals (LC) and their resulting rheological behavior are presented. The effects of different variables are addressed: CNC aspect ratio, surface chemistry, concentration, time required for the appearance of an anisotropic phase and addition of other components to the suspension media. The changes on the structure induced by alignment, and by conditions of the drying process are also reported. The optical properties of the films are considered, and the effect of the above variables on the final transparency, iridescence and overall optical response of these bio-inspired photonic materials. Control of the reviewed variables is needed to achieve reliable materials in applications such as sensors, smart inks and papers, transparent flexible supports for electronics, decorative coatings and films.

EPR spectroscopy applied to the study of the TEMPO mediated oxidation of nanocellulose.

Two different methods of pH control were used in the synthesis of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) oxidized cellulose nanocrystals (CNC) and the reaction kinetics and degree of oxidation were investigated. In method I the media pH was controlled by addition of NaOH solution. The effect of the oxidant concentration (sodium hypochloride, NaClO) on the final degree of oxidation and crystallinity of the samples was investigated. Conditions for obtaining an optimum balance between high crystallinity and degree of oxidation were selected from those results. In method II, pH was fixed by using a buffer solution. Electron spin resonance (ESR) spectroscopy offered direct information of the decay of TEMPO concentration under these conditions. The kinetics of the reaction was determined, finding a direct correlation between these results and those corresponding to the decay of the NaClO concentration and the advance of the CNC degree of oxidation. Differences found between the two methods were analyzed.

Polyelectrolyte films based on chitosan/olive oil and reinforced with cellulose nanocrystals.

Composite films designed as potentially edible food packaging were prepared by casting film-forming emulsions based on chitosan/glycerol/olive oil containing dispersed cellulose nanocrystals (CNs). The combined use of cellulose nanoparticles and olive oil proved to be an efficient method to reduce the inherently high water vapor permeability of plasticized chitosan films, improving at the same time their tensile behavior. At the same time, it was found that the water solubility slightly decreased as the cellulose content increased, and further decreased with oil addition. Unexpectedly, opacity decreased as cellulose content increased, which balanced the reduced transparency due to lipid addition. Contact angle decreased with CN addition, but increased when olive oil was incorporated. Results from dynamic mechanical tests revealed that all films present two main relaxations that could be ascribed to the glycerol- and chitosan-rich phases, respectively. The response of plasticized chitosan-nanocellulose films (without lipid addition) was also investigated, in order to facilitate the understanding of the effect of both additives.