Bioinspired Catecholic Flame Retardant Nanocoating for Flexible Polyurethane Foams

An efficient, environmentally friendly, and water-applied flame retardant surface nanocoating based on polydopamine (PDA) was developed for foamed materials such as polyurethane (PU). The PDA nanocoating, deposited by simple dip-coating in an aqueous dopamine solution, consists of a planar sublayer and a secondary granular layer structure that evolve together, eventually turning into a dense, uniform, and conformal layer on all foam surfaces. In contrast to flexible PU foams that are known to be highly flammable without flame retardant additives, micro combustion calorimetry (MCC) and thermogravimetric analysis (TGA) confirm that the neat PDA is relatively inflammable with a strong tendency to form carbonaceous, porous char that is highly advantageous for flame retardancy. By depositing nanocoatings of PDA onto flexible PU foams, the flammability of the PU foam was significantly reduced with increasing coating thickness. For the thickest coating (3 days of PDA deposition), the foam quickly self-extinguished and its original shape was completely preserved after exposure to a flame in a torch burn test. In addition to the char forming ability of PDA, it is hypothesized that its catechol units likely scavenge nearby radicals that typically evolve additional fuel for the fire as they attack surrounding materials. This multiple flame retardancy action of PDA (i.e., char formation + radical scavenging) enables flame retardant foams with a peak heat release rate (P-HRR) that is significantly reduced (up to 67%) relative to control foams, representing much better performance than many conventional additives reported in the literature at comparable or higher loadings

High-Affinity DNA Base Analogs as Supramolecular, Nanoscale Promoters of Macroscopic Adhesion

Adhesion phenomena are essential to many biological processes and to synthetic adhesives and manufactured coatings and composites. Supramolecular interactions are often implicated in various adhesion mechanisms. Recently, supramolecular building blocks, such as synthetic DNA base-pair mimics, have drawn attention in the context of molecular recognition, self-assembly, and supramolecular polymers. These reversible, hydrogen-bonding interactions have been studied extensively for their adhesive capabilities at the nano- and microscale, however, much less is known about their utility for practical adhesion in macroscopic systems. Herein, we report the preparation and evaluation of supramolecular coupling agents based on high-affinity, high-fidelity quadruple hydrogen-bonding units (e.g., DAN·DeUG, <i>K</i>_assoc = 10⁸ M^–1 in chloroform). Macroscopic adhesion between polystyrene films and glass surfaces modified with 2,7-diamidonaphthyridine (DAN) and ureido-7-deazaguanine (DeUG) units was evaluated by mechanical testing. Structure–property relationships indicate that the designed supramolecular interaction at the nanoscale plays a key role in the observed macroscopic adhesive response. Experiments probing reversible adhesion or self-healing properties of bulk samples indicate that significant recovery of initial strength can be realized after failure but that the designed noncovalent interaction does not lead to healing during the process of adhesion loss

Marangoni Instability Driven Surface Relief Grating in an Azobenzene-Containing Polymer Film

The Marangoni effect describes fluid flow near an interface in response to a surface tension gradient. Here, we demonstrate that the Marangoni effect is the underlying mechanism for flow driven feature formation in an azobenzene-containing polymer film; features formed in azobenzene-containing polymers are often referred to as surface relief gratings or SRGs. An amorphous poly­(4-(acryloyl­oxyhexyl­oxy)-4′-pentyl­azobenzene) was synthesized and studied as a model polymer. To isolate the surface tension driven flow from the surface tension pattern inscription step, the surface tension gradient was preprogrammed via photoisomerization of azobenzene in a glassy polymer film without forming topographical features. Subsequently, the latent image was developed in the absence of light by annealing above the glass transition temperature where the polymer is a liquid. The polymer flow direction was controlled with precision by inducing different surface tension changes in the exposed regions, in accordance with expectation based on the Marangoni effect. Finally, the height of the formed features decreased upon extensive thermal annealing due to capillary leveling with two distinct rates. A scaling analysis revealed that those rates originated from dissimilar capillary velocities associated with different azobenzene isomers