Sustainable water responsive mechanically adaptive and self-healable polymer composites derived from biomass

Abstract

New synthetic biobased mechanically adaptive composites, responding to water and having self-healing property, were developed. These composites were prepared by introducing plant-based cellulose nanofibrils (CNFs) at 10, 20, and 25% (v/v) concentration into a biobased rubbery poly (myrcene-co-furfuryl methacrylate) (PMF) matrix by solution mixing and subsequent compression molding technique. The reinforcement of CNFs led to an increase in the tensile storage modulus (E’) of the dry composites. Upon exposure to water, water sensitivity and a drastic fall in storage moduli (E’) were observed for the 25% (v/v) CNF composite. A modulus reduction from 1.27 (dry state) to 0.15 MPa (wet state) was observed for this composite. The water-sensitive nature of the composites was also confirmed from the force modulation study in atomic force microscopy (AFM), revealing the average modulus as 82.7 and 32.3 MPa for dry and swollen composites, respectively. Interestingly, the composites also showed thermoreversibility and excellent healing property via Diels-Alder (DA) click chemistry using bismaleimide as a crosslinker, when the scratched samples were heated at 120◦C (rDA) for 10 h and then cooled down to 60◦C (DA) followed by room temperature. The healing efficiency was obtained as about 90% from the AFM 3D height images. Thus, the composites exhibited dual stimuli-responsive behavior as mechanically adaptive water sensitive polymers with water as the stimulus and self-healing polymer using bismaleimide as an external stimulus. Therefore, this study provides guidance and new frontiers to make use of composite materials based on biopolymers for various potential smart and biomedical applications.