Sustainable circular economy requires materials that possess a property profile comparable to synthetic polymers and, additionally, processing and sourcing of raw materials that have a small environmental footprint. Here, we present a paradigm for processing marine biopolymers into materials that possess both elastic and plastic behavior within a single system involving a double-interpenetrating polymer network comprising the elastic phase of dynamic physical cross-links and stress-dissipating ionically cross-linked domains. As a proof of principle, films possessing more than twofold higher elastic modulus, ultimate tensile strength, and yield stress than those of polylactic acid were realized by blending two water-soluble marine polysaccharides, namely alginic acid (Alg) with physically cross-linkable carboxylated agarose (CA) followed by ionic cross-linking with a divalent cation. Dried CAAlg films showed homogeneous nano-micro-scale domains, with yield stress and size of the domains scaling inversely with calcium concentration. Through surface activation/cross-linking using calcium, CAAlg films could be further processed using wet bonding to yield laminated structures with interfacial failure loads (13.2 ± 0.81 N) similar to the ultimate loads of unlaminated films (10.09 ± 1.47 N). Toward the engineering of wood-marine biopolymer composites, an array of lines of CAAlg were printed on wood veneers (panels), dried, and then bonded following activation with calcium to yield fully bonded wood two-ply laminate. The system presented herein provides a blueprint for the adoption of marine algae-derived polysaccharides in the development of sustainable high-performance materials.
Keywords: 3D printing; bio-nanocomposite; circular economy; double-interpenetrating network; nanostructured domains.