Macroscopic Self-Assembly Realized by Polymer Brush―A Thickness-Dependent Rule for Rapid Wet Adhesion

Macroscopic self-assembly of mu m-to-mm components (dimension from 100 mu m to millimeters), is meaningful to realize the concept of "self-assembly at all scales" and to understand interfacial phenomena such as adhesion, self-healing, and adsorption. However, self-assembly at this length scale is different from molecular self-assembly due to limited collision chances and binding capacity between components. Long-time contact between components is requisite to realize mu m-to-mm assembly. Even though the recent idea of adding a compliant coating to enhance the molecular binding capacity is effective for such self-assembly, a trade-off between coating thickness (several micrometers) and assembly efficiency exists. Here a new compliant coating of surface-initiated polymer brush to address the above paradox by both realizing fast assembly and reducing the coating thickness to approximate to 40 nm by two magnitudes is demonstrated. Millimeter-sized quartz cubes are used as components and grafted with oppositely charged polyelectrolyte brushes, enabling assembly in water by electrostatic attraction and disassembly in NaCl solutions. A rule of thickness-dependent assembly chance is obtained and understood by in situ force measurements and a multivalent theory. The polymer brush strategy pushes the thickness limit of requisite compliant coating to the nanoscale for fast mu m-to-mm self-assembly and provides insights into rapid wet adhesion. Surface-initiated (SI) polyelectrolyte brush is used as a compliant coating to promote interfacial binding and realize fast self-assembly of mu m-to-mm hard materials (quartz) in seconds. Owing to the flexibility of the SI brush, the lower thickness limit of requisite compliant coatings is reduced by two magnitudes from 3-4 mu m to 40 nm, which is meaningful for fast wet adhesion. image