The use of maleinized (MLO) and epoxidized (ELO) linseed oils as potential biobased plasticizers for lignin/natural fiber composites formulations with improved toughness was evaluated. Arboform®, a lignin/natural fiber commercial composite, was used as a reference matrix for the formulations. The plasticizer content varied in the range 0–15 wt % and mechanical, thermal and morphological characterizations were used to assess the potential of these environmentally friendly modifiers. Results from impact tests show a general increase in the impact-absorbed energy for all the samples modified with bio-oils. The addition of 2.5 wt % of ELO to Arboform (5.4 kJ/m2) was able to double the quantity of absorbed energy (11.1 kJ/m2) and this value slightly decreased for samples containing 5 and 10 wt %. A similar result was obtained with the addition of MLO at 5 wt %, with an improvement of 118%. The results of tensile and flexural tests also show that ELO and MLO addition increased the tensile strength as the percentage of both oils increased, even if higher values were obtained with lower percentages of maleinized oil due to the possible presence of ester bonds formed between multiple maleic groups present in MLO and the hydroxyl groups of the matrix. Thermal characterization confirmed that the mobility of polymer chains was easier in the presence of ELO molecules. On the other hand, MLO presence delayed the crystallization event, predominantly acting as an anti-nucleating agent, interrupting the folding or packing process. Both chemically modified vegetable oils also efficiently improved the thermal stability of the neat matrix.
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