Magnetic cellulose nanocrystal nanocomposites for the development of green functional materials.

A magnetic cellulosic material composed of cellulose nanocrystals (CNC) and cobalt ferrite (CoFe2O4) nanoparticles was developed through evaporation-induced self-assembly (EISA). Nanoparticles demonstrated good dispersibility within the cellulose nanocrystal template. The addition of glucose to CNC network allows the development of homogeneous crack-free CNC-based films and does no modify neither the morphology nor the optical properties. In contrast, the introduction of CoFe2O4 nanoparticles produces a marked decrease in the amount of the transmitted light. 20wt.% of CoFe2O4 nanoparticles inside the CNC matrix induced a maximum magnetization value of 12.96emug-1, increased the real part of the dielectric constant (permittivity) from 10 (pure CNC film) to 12 and improved the thermostability of the nanocomposite as evidenced by the increase of the onset temperature from 165.1 to 220.4°C. Those features obtained in a non-petroleum-based composite provide insight into the development of the next generation of functional materials from natural origin.

Thermal stability increase in metallic nanoparticles-loaded cellulose nanocrystal nanocomposites.

Due to the potential of CNC-based flexible materials for novel industrial applications, the aim of this work is to improve the thermal stability of cellulose nanocrystals (CNC) films through a straightforward and scalable method. Based of nanocomposite approach, five different metallic nanoparticles (ZnO, SiO2, TiO2, Al2O3 and Fe2O3) have been co-assembled in water with CNCs to obtain free-standing nanocomposite films. Thermogravimetric analysis (TGA) reveals an increased thermal stability upon nanoparticle. This increase in the thermal stability reaches a maximum of 75°C for the nanocomposites having 10wt% of Fe2O3 and ZnO. The activation energies of thermodegradation process (Ea) determined according to Kissinger and Ozawa-Flynn-Wall methods further confirm the delayed degradation of CNC nanocomposites upon heating. Finally, the changes induced in the crystalline structure during thermodegradation were followed by wide angle X-ray diffraction (WAXD). It is also observed that thermal degradation proceeds at higher temperatures for nanocomposites having metallic nanoparticles. Overall, experimental findings here showed make nanocomposite approach a simple low-cost environmentally-friendly strategy to overcome the relatively poor thermal stability of CNCs when extracted via sulfuric acid assisted hydrolysis of cellulose.

Poly(L-lactide)/branched ß-cyclodextrin blends: Thermal, morphological and mechanical properties.

In this work we develop poly(L-lactide)/branched ß-cyclodextrin (bßCD) blends in an attempt to obtain new biocompatible and biodegradable materials to be used in the emerging fields of pharmaceutical, biomedicine and food industry. Ionic branched ß-cyclodextrin (bßCD) was obtained by polycondensation of the ß-CD monomer and it was blended with a commercially available PLLA. Fourier transform infrared spectroscopy (FTIR) has been applied to study the occurring interactions between both partners. Thermal properties of blends have been analyzed by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), while the phase structure of the blends was analyzed by scanning electron microscopy (SEM). Finally, dynamic mechanical analysis (DMA) has been used to provide further insights into the features controlling miscibility between PLLA and bßCD. Results show the presence of a single phase irrespectively of the blend composition. Overall, this work opens new perspectives for the development of naturally available materials with tunable functional properties for applications in which cyclodextrins emerge as a new class of promising candidates.

Increased functional properties and thermal stability of flexible cellulose nanocrystal/ZnO films.

In this work we attempt to improve the functional properties and thermal stability of cellulose nanocrystal (CNC) films by means of eco-friendly materials and processes. Mechanically flexible films of closely packed CNCs with concentrations up to 5 wt.% of zinc oxide (ZnO) nanoparticles have been prepared by a simple, standard and environmentally friendly method using solely water. Results reveal that ultraviolet light is blocked by 98.5% at 1 wt.% ZnO while good transparency is maintained. A sharp hydrophobicity increase is observed with the addition of ZnO which would enhance the durability of films by decreasing the water diffusion through the material. The thermal degradation activation energy (E) presents an increase of 141%, denoting a high thermal stability of films, which would result beneficial for their potential application in the field of flexible electronics. Mechanical results demonstrate a high structural integrity of CNC/ZnO as a result of the occurring strong cellulosic inter- and intramolecular interactions within the closely packed CNC network. In overall, this work highlights the potential for environmentally friendly processing of sustainable nanostructured functional materials based on cellulose.

Crystallization, structural relaxation and thermal degradation in Poly(L-lactide)/cellulose nanocrystal renewable nanocomposites.

In this work, crystallization, structural relaxation and thermal degradation kinetics of neat Poly(L-lactide) (PLLA) and its nanocomposites with cellulose nanocrystals (CNC) and CNC-grafted-PLLA (CNC-g-PLLA) have been studied. Although crystallinity degree of nanocomposites remains similar to that of neat homopolymer, results reveal an increase on the crystallization rate by 1.7-5 times boosted by CNC, which act as nucleating agents during the crystallization process. In addition, structural relaxation kinetics of PLLA chains has been drastically reduced by 53% and 27% with the addition of neat and grafted CNC, respectively. The thermal degradation activation energy (E) has been determined from thermogravimetric analysis in the light of Kissinger's and Ozawa-Flynn-Wall theoretical models. Results reveal a reduction on the thermal stability when in presence of CNC-g-PLLA, while raw CNC slightly increases the thermal stability of PLLA. Fourier transform infrared spectroscopy and energy dispersive X-ray spectroscopy results confirm that the presence of residual catalyst in CNC-g-PLLA plays a pivotal role in the thermal degradation behavior of nanocomposites.

Study of the chain microstructure effects on the resulting thermal properties of poly(L-lactide)/poly(N-isopropylacrylamide) biomedical materials.

The development of thermally-sensitive poly(N-isopropylacrylamide) (PNIPAAm) and biocompatible/biodegradable poly(L-lactide) (PLLA) blends offers us an efficient strategy in order to obtain materials with improved functional properties to be used in the emerging field of biomedicine. In this sense, thermal properties of PLLA and PNIPAAm have been investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and wide angle X-ray diffraction (WAXD) were conducted to shed more light on the obtained results. For a better understanding of PLLA/PNIPAAm system, both low and high molecular weight PLLA and PNIPAAm have been synthesized by ring opening polymerization and aqueous redox polymerization respectively. Obtained results are interpreted from the viewpoint of chain microstructure of each homopolymer and the ratio between two constituent materials. DSC, SEM and WAXD results show a phase separation over the entire composition range irrespectively of the molecular weight of both homopolymers. Additionally, it was found a nucleating agent behavior of low molecular weight PNIPAAm, while high molecular weight PNIPAAm hinders the crystallization of PLLA. FTIR results suggest that the strong autoassociation present in PNIPAAm plays a key role impairing the miscibility of the whole system. Thermogravimetric analysis reveals that thermodegradation process of PLLA could be continuously delayed with the addition of PNIPAAm due to the increased thermal stability of N-isopropylacrylamide in regard to L-lactide sequences.