Benchmarking supramolecular adhesive behavior of nanocelluloses, cellulose derivatives and proteins.

One of the key steps towards a broader implementation of renewable materials is the development of biodegradable adhesives that can be attained at scale and utilized safely. Recently, cellulose nanocrystals (CNCs) were demonstrated to have remarkable adhesive properties. Herein, we study three classes of naturally synthesized biopolymers as adhesives, namely nanocelluloses (CNFs), cellulose derivatives, and proteins by themselves and when used as additives with CNCs. Among the samples evaluated, the adhesion strength was the highest for bovine serum albumin and hydroxypropyl cellulose (beyond 10 MPa). These were followed by carboxymethylcellulose and CNCs (ca. 5 MPa) and mechanically fibrillated CNFs (ca. 2 MPa), and finally by tempo-oxidized CNFs (0.2 MPa) and lysozyme (1.5 MPa). Remarkably, we find that the anisotropy of adhesion (in plane vs out of plane) falls within a narrow range across the bio-based adhesives studied. Collectively, this study benchmarks bio-based non-covalent adhesives aiming towards their improvement and implementation.

Chitin-amyloid synergism and their use as sustainable structural adhesives.

Structural adhesives are relevant to many engineering applications, especially those requiring load-bearing joints with high lap shear strength. Typical adhesives are synthesized from acrylics, epoxies, or urethanes, which may pose a burden to sustainability and the environment. In nature, the interfacial interactions between chitin and proteins are used for structural purposes and as a bio-cement, resulting in materials with properties unmatched by their man-made counterparts. Herein, we show that related supramolecular interactions can be harnessed to develop high strength green adhesives based on chitin nanocrystals (ChNCs), isolated from shrimp shells, and hen egg white lysozyme (HEWL) used in its monomeric or amyloid forms. Consolidation of the bicomponent suspensions, placed between glass substrates, results in long-range ordered superstructures. The formation of these structures is evaluated by surface energy considerations, followed by scanning electron, atomic force, and polarized microscopies of the consolidated materials. For 0.8 mg of bio-adhesive (lysozyme, ChNCs or their composites), lap shear loads of over 300 N are reached. Such remarkable adhesion reaches maximum values at protein-to-ChNC ratios below 1 : 4, reflecting the synergy established between the components (ca. 25% higher load compared to ChNCs, the strongest single component). We put the observed adhesive performance in perspective by comparing the lap-shear performance with current research on green supramolecular adhesives using natural biopolymers. The results are discussed in the context of current efforts to standardize the measurement of adhesive strength and bond preparation. The latter is key to formalizing the metrology and materials chemistry of bio-based adhesives. The proposed all-green system is expected to expand current developments in the design of bio-based adhesives.