Interfacial interactions governing the interfacial adhesion between cellulose propionate and carbon fibre surface are placed under scrutiny to pave the way towards the development of green cellulose-based carbon fibre reinforced polymers. A range of molecular entities are deposited on the surface by initially grafting aromatic structures with appropriate functions via diazonium species followed by further derivatization of these entities. Cellulose propionate was also bound covalently to the surface via a tosylated derivative invoking its facile nucleophilic displacement reaction with surface-grafted amino functions. Significant increase in interfacial shear strength was obtained for the cellulose propionategrafted carbon fibre composite as well as for the 4-(aminomethyl)benzene-functionalized sample, in the latter case possible hydrogen bonding took place with the cellulose propionate matrix. Furthermore, the positive effect of a highly lipophilic and yet compact -CF 3 substituent was also noted. In order to let the grafted structure efficiently penetrate into the matrix, steric factors, lipophilicity and potential secondary interactions should be considered. It needs to be pointed out that we provide the first synthetic strategy to covalently bind cellulose derivatives to a largely graphitic surface and as such, it has relevance to carbonaceous materials being applied in cellulose-based innovative materials in the future.

While intensive efforts are made to prepare carbon fiber reinforced plastics from renewable sources, less emphasis is directed towards elaborating green approaches for carbon fiber surface modification to improve the interfacial adhesion in these composites. In this study, we covalently attach lignin, a renewable feedstock, to a graphitic surface for the first time. The covalent bond is established via aromatic anchoring groups with amine functions taking part in a nucleophilic displacement reaction with a tosylated lignin derivative. The successful grafting procedures were confirmed by cyclic voltammetry, X-ray photoelectron spectroscopy, and field emission scanning electron microscopy coupled with energy dispersive X-ray spectroscopy. Both fragmentation and microdroplet tests were conducted to evaluate the interfacial shear strength of lignin coated carbon fiber samples embedded in a green cellulose propionate matrix and in a commercially used epoxy resin. The microdroplet test showed ~27% and ~65% increases in interfacial shear strength for the epoxy and cellulose propionate matrix, respectively. For the epoxy matrix covalent bond, it is expected to form with lignin, while for the cellulosic matrix hydrogen bond formation might take place; furthermore, plastisizing effects are also considered. Our study opens the gates for utilizing lignin coating to improve the shear tolerance of innovative composites.

Carbon fiber reinforced composites have exceptional potential to play a key role in the materials world of our future. However, their success undoubtedly depends on the extent they can contribute to advance a global sustainability objective. Utilizing polymers in these composites that can be potentially derived from biomasses would be certainly vital for next-generation manufacturing practices. Nevertheless, deep understanding and tailoring fiber-matrix interactions are crucial issues in order to design carbon fiber reinforced sustainable resource-based biocomposites. In this study, cellulose derivatives (cellulose propionate and cellulose acetate butyrate) are utilized as model polymer matrices that can be potentially fabricated from biomasses, and the mechanical properties of the prepared short carbon fiber reinforced composites are engineered by means of a functional biobased lignin coating on the fiber surface. Furthermore, polyamide 6 based composites are also prepared, the monomer of this polymer could be obtained using C6 sugars derived from lignocellulosic biomasses in the future (through 5-hydroxymethylfurfural). Lignin was successfully immobilized on the carbon fiber surface via an industrially scalable benign epoxidation reaction. The surface modification had a beneficial impact on the mechanical properties of cellulose propionate and polyamide 6 composites. Furthermore, our results also revealed that cellulose-based matrices are highly sensitive to the presence of rigid fiber segments that restrict polymer chain movements and facilitate stress development. It follows that the physicochemical properties of the cellulosic matrices (molecular weight, crystallinity), associated with polymer chain mobility, might need to be carefully considered when designing these composites. At the same time, polyamide 6 showed excellent ability to accommodate short carbon fibers without leading to a largely brittle material, in this case, a maximum tensile strength of ~136 MPa was obtained at 20 wt% fiber loading. These results were further contrasted with that of a petroleum-based polypropylene matrix exhibiting inferior mechanical properties. Our study clearly indicates that carbon fiber reinforced polymers derived and designed using biomass-derived resources can be promising green materials for a sustainable future.

To become independent of petroleum resources, societies have to develop methods to synthesize full-biobased polymers from natural products directly. In this study, full-biobased cellulose esters were synthesized by the oxidative esterification process between cellulose and natural α,β-unsaturated aldehydes in an ionic liquid working as solvent and catalyst. The role of the ionic liquid in this cellulose-modification system was systematically investigated, and a newly designed noncarboxylate-type ionic liquid, 1-ethyl-3-methylimidazolium 2-pyridinolate (EmimOPy), was developed to prevent a serious side reaction in which the carboxylate anion of the carboxylate-type ionic liquid is introduced into the hydroxyl group of cellulose as an ester group on the products. Under optimized conditions, this oxidative esterification-reaction system in EmimOPy afforded fully substituted cellulose ester (up to the degree of substitution = 3.0). Furthermore, cellulose reacted with several types of aldehyde substrates, even biobased low-reactive α- or β-substituted unsaturated aldehydes (e.g., citral and perillaldehyde). Thus, this synthesis demonstrates excellent atom economy without using any additional catalysts or activators under metal-free conditions.

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