Cooperativity of Catechols and Amines in High-Performance Dry/Wet Adhesives.

The outstanding adhesive performance of mussel byssal threads has inspired materials scientists over the past few decades. Exploiting the amino-catechol synergy, polymeric pressure-sensitive adhesives (PSAs) have now been synthesized by copolymerizing traditional PSA monomers, butyl acrylate and acrylic acid, with mussel-inspired lysine- and aromatic-rich monomers. The consequences of decoupling amino and catechol moieties from each other were compared (that is, incorporated as separate monomers) against a monomer architecture in which the catechol and amine were coupled together in a fixed orientation in the monomer side chain. Adhesion assays were used to probe performance at the molecular, microscopic, and macroscopic levels by a combination of AFM-assisted force spectroscopy, peel and static shear adhesion. Coupling of catechols and amines in the same monomer side chain produced optimal cooperative effects in improving the macroscopic adhesion performance.

Enhanced Adhesion and Cohesion of Bioinspired Dry/Wet Pressure-Sensitive Adhesives.

The byssus-mediated adhesion of marine mussels is a widely mimicked system for robust adhesion in both dry and wet conditions. Mussel holdfasts are fabricated from proteins that contain a significant amount of the unique catecholic amino acid dihydroxyphenylalanine, which plays a key role in enhancing interfacial adhesion to organic and inorganic marine surfaces and contributes to cohesive strength of the holdfast. In this work, pressure-sensitive adhesives (PSAs) were synthesized by copolymerization of dopamine methacrylamide (DMA) with common PSA monomers, butyl acrylate and acrylic acid, with careful attention paid to the effects of catechol on adhesive and cohesive properties. A combination of microscopic and macroscopic adhesion assays was used to study the effect of catechol on adhesion performance of acrylic PSAs. Addition of only 5% DMA to a conventional PSA copolymer containing butyl acrylate and acrylic acid resulted in 6-fold and 2.5-fold increases in work required to separate the PSA from silica and polystyrene, respectively, and a large increase in 180° peel adhesion against stainless steel after 24 h storage in both ambient and underwater conditions. Moreover, the holding power of the catechol PSAs on both steel and high-density polyethylene under shear load continuously increased as a function of catechol concentration, up to a maximum of 10% DMA. We also observed stark increases in shear and peel adhesion for the catecholic adhesives over PSAs with noncatecholic aromatic motifs, further underlining the benefits of catechols in PSAs. Overall, catechol PSAs perform extremely well on polar and metallic surfaces. The advantage of incorporating catechols in PSA formulations, however, is less straightforward for peel adhesion in nonpolar, organic substrates and tackiness of the PSAs.