Abstract. Current challenges highlight the need for polymer research using renewable natural sources as a substitute for petroleum-based polymers. The use of polyols obtained from renewable sources combined with the reuse of industrial residues such as lignin is an important agent in this process. Different compositions of polyurethane-type materials were prepared by combining technical Kraft lignin (TKL) with castor oil (CO) or modified castor oil (MCO1 and MCO2) to increase their reactivity towards diphenylmethane diisocyanate (MDI). The results indicate that lignin increases the glass transition temperature, the crosslinking density and improves the ultimate stress especially for those prepared from MCO2 and 30% lignin content from 8.2 MPa (lignin free) to 23.5 MPa. Scanning electron microscopy (SEM) micrographs of rupture surface after uniaxial tensile tests show ductile-to-brittle transition. The results show the possibility to develop polyurethane-type materials, varying technical grade Kraft lignin content, which cover a wide range of mechanical properties (from large elastic/low Young modulus to brittle/high Young modulus polyurethanes).

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New techniques to manipulate the electronic properties of few layer 2D materials, unveiling new physical phenomena as well as possibilities for new device applications have brought renewed interest to these systems. Therefore, the quest for reproducible methods for the large scale synthesis, as well as the manipulation, characterization and deeper understanding of these structures is a very active field of research. We here report the production of nitrogen doped bilayer graphene in a fast single step (2.5 minutes), at reduced temperatures (760 °C) using microwave plasma-enhanced chemical vapor deposition (MW-PECVD). Raman spectroscopy confirmed that nitrogen-doped bilayer structures were produced by this method. XPS analysis showed that we achieved control of the concentration of nitrogen dopants incorporated into the final samples. We have performed state of the art parameter-free simulations to investigate the cause of an unexpected splitting of the XPS signal as the concentration of nitrogen defects increased. We show that this splitting is due to the formation of interlayer bonds mediated by nitrogen defects on the layers of the material. The occurrence of these bonds may result in very specific electronic and mechanical properties of the bilayer structures.

Several efforts have been dedicated to the development of lignin-based polyurethanes (PU) in recent years. The low and heterogeneous reactivity of lignin hydroxyl groups towards diisocyanates, arising from their highly complex chemical structure, limits the application of this biopolymer in PU synthesis. Besides the well-known differences in the reactivity of aliphatic and aromatic hydroxyl groups, experimental work in which the reactivity of both types of hydroxyl, especially the aromatic ones present in syringyl (S-unit), guaiacyl (G-unit), and p-hydroxyphenyl (H-unit) building units are considered and compared, is still lacking in the literature. In this work, the hydroxyl reactivity of two kraft lignin grades towards 4,4′-diphenylmethane diisocyanate (MDI) was investigated. 31P NMR allowed the monitoring of the reactivity of each hydroxyl group in the lignin structure. FTIR spectra revealed the evolution of peaks related to hydroxyl consumption and urethane formation. These results might support new PU developments, including the use of unmodified lignin and the synthesis of MDI-functionalized biopolymers or prepolymers.