Effective reinforcement of plasticized starch by the incorporation of graphene, graphene oxide and reduced graphene oxide.

Plasticized starch (PLS) nanocomposite films using glycerol and reinforced with graphene (G) and graphene oxide (GO) were prepared by solvent casting procedure. On one hand, the influence of adding different G contents into the PLS matrix was analyzed. In order to improve the stability of G nanoflakes in water, Salvia extracts were added as surfactants. The resulting nanocomposites presented improved mechanical properties. A maximum increase of 287 % in Young's modulus and 57 % in tensile strength was achieved for nanocomposites with 5 wt% of G. However, it seemed that Salvia acted as co-plasticizer for the PLS. Moreover, the addition of the highest G content led to an improvement of the electrical conductivity close to 5 × 10-6 S/m compared to the matrix. On the other hand, GO was also incorporated as nanofiller to prepare nanocomposites. Thus, the effect of increasing the GO content in the final behavior of the PLS nanocomposites was evaluated. The characterization of GO containing PLS nanocomposites showed that strong starch/GO interactions and a good dispersion of the nanofiller were achieved. Moreover, the acidic treatment applied for the reduction of the GO was found to be effective, since the electrical conductivity was 150 times bigger than its G containing counterpart.

Enhancing the Mechanical Properties of 3D-Printed Waterborne Polyurethane-Urea and Cellulose Nanocrystal Scaffolds through Crosslinking.

In this work, shape-customized scaffolds based on waterborne polyurethane-urea (WBPUU) were prepared via the combination of direct ink writing 3D-printing and freeze-drying techniques. To improve the printing performance of the ink and guarantee a good shape fidelity of the scaffold, cellulose nanocrystals (CNC) were added during the synthesis of the WBPUU and some of the printed constructs were immersed in CaCl2 prior to the freeze-drying process to promote ionic crosslinking between calcium ions and the polyurethane. The results showed that apart from allowing the ink to be successfully printed, obtaining scaffolds with good shape fidelity, the addition of the CNC resulted in a greater homogeneity of the porous structure as well as an increase of the swelling capacity of the scaffolds. Additionally, the CNC has a reinforcement effect in the printed systems, presenting a higher compression modulus as the CNC content increases. In the case of samples crosslinked by calcium ions, a rigid shell was observed by scanning electron microscopy, which resulted in stiffer scaffolds that presented a lower water absorption capacity as well as an enhancement of the thermal stability. These results showed the potential of this type of post-printing process to tune the mechanical properties of the scaffold, thus widening the potential of this type of material.

Effect of Cellulose Nanofibers' Structure and Incorporation Route in Waterborne Polyurethane-Urea Based Nanocomposite Inks.

In order to continue the development of inks valid for cold extrusion 3D printing, waterborne, polyurethane-urea (WBPUU) based inks with cellulose nanofibers (CNF), as a rheological modulator, were prepared by two incorporation methods, ex situ and in situ, in which the CNF were added after and during the synthesis process, respectively. Moreover, in order to improve the affinity of the reinforcement with the matrix, modified CNF was also employed. In the ex situ preparation, interactions between CNFs and water prevail over interactions between CNFs and WBPUU nanoparticles, resulting in strong gel-like structures. On the other hand, in situ addition allows the proximity of WBPUU particles and CNF, favoring interactions between both components and allowing the formation of chemical bonds. The fewer amount of CNF/water interactions present in the in situ formulations translates into weaker gel-like structures, with poorer rheological behavior for inks for 3D printing. Stronger gel-like behavior translated into 3D-printed parts with higher precision. However, the direct interactions present between the cellulose and the polyurethane-urea molecules in the in situ preparations, and more so in materials reinforced with carboxylated CNF, result in stronger mechanical properties of the final 3D parts.

Reprogrammable Permanent Shape Memory Materials Based on Reversibly Crosslinked Epoxy/PCL Blends.

: Epoxy/Polycaprolactone (PCL) blends cured with a conventional diamine (4,4'-diaminodiphenylmethane, DDM) and with different amounts of a disulfide containing diamine (4, 4´-dithioaniline, DSS) were prepared through melting. The curing process was studied by FTIR and differential scanning calorimetry (DSC) and the mechanical behavior of the networks was studied by DMA. The shape memory properties and the recyclability of the materials were also analyzed. All blends showed a very high curing degree and temperature activated shape memory effect, related to the glass transition of the epoxy resin. The PCL plasticized the mixture, allowing tailoring of the epoxy glass transition. In addition, in the blends cured with DSS, as a consequence of the disulfide exchange reaction, the permanent shape could be erased and a new shape could be reprogrammed. Using this strategy, reprogrammable permanent shape memory materials were obtained.

Analysis of the Process Parameters for Obtaining a Stable Electrospun Process in Different Composition Epoxy/Poly ε-Caprolactone Blends with Shape Memory Properties.

In this work Poly ε-caprolactone (PCL)/ Diglycidyl ether of bisphenol A (DGEBA) blends were electrospun and the obtained mats were UV cured to achieve shape memory properties. In the majority of studies, when blends with different compositions are electrospun, the process variables such as voltage or flow rate are fixed independently of the composition and consequently the quality of the fibers is not optimized in all of the range studied. In the present work, using the design of experiments methodology, flow rate and voltage required to obtain a stable process were evaluated as responses in addition to the fiber diameter and shape memory properties. The results showed that the solution concentration and amount of PCL played an important role in the voltage and flow rate. For the shape memory properties excellent values were achieved and no composition dependence was observed. In the case of fiber diameter, similar results to previous works were observed.

The role of cellulose nanocrystals incorporation route in waterborne polyurethane for preparation of electrospun nanocomposites mats.

Electrospinning offers the possibility of obtaining fibers mats from polymer solutions. The use of environmentally-friendly waterborne polyurethane (WBPU) allows obtaining electrospun polyurethane mats in water medium. Furthermore, the incorporation of water dispersible nanoentities, like renewable cellulose nanocrystals (CNC), is facilitated. Therefore, in this work, a WBPU was synthesized and CNC were isolated for preparing WBPU-CNC dispersions nanocomposites with 1 and 3wt% of CNC following both the classical mixing by sonication, and the innovative in-situ route. The dispersions were used for obtaining electrospun mats assisted by poly(ethylene oxide) (PEO) as polymer template. Moreover, the extraction of PEO with water resulted in continuous WBPU-CNC mats, showing different properties respect to WBPU-CNC mats containing PEO. The effective addition of CNC led to more defined cylindrical morphologies and the two alternative incorporation routes induced to different CNC dispositions in the matrix, which modified fibers diameters, and thus, mats final properties.