Recruiting physisorbed water in surface polymerization for bio-inspired materials of tunable hydrophobicity†
Chemical grafting has been widely used to modify the surface properties of materials, especially surface energy for controlled wetting, because of the resilience of such coatings/modifications. Reagents with multiple reactive sites have been used with the expectation that a monolayer will form. The step-growth polymerization mechanism, however, suggests the possibility of gel formation for hydrolyzable moieties in the presence of physisorbed water. In this report, we demonstrated that using alkyltrichlorosilanes (trivalent [i.e., 3 reactive sites]) in the surface modification of a cellulosic material (paper) does not yield a monolayer but rather gives surface-bound particles. We infer that the presence of physisorbed (surface-bound) water allows for polymerization (or oligomerization) of the silane prior to its attachment on the surface. Surface energy mismatch between the hydrophobic tails of the growing polymer and any unreacted bound water leads to the assembly of the polymerizing material into spherical particles to minimize surface tension. By varying paper grammage (16.2–201.4 g m−2), we varied the accessible surface area and thus the amount of surface-adsorbed water, allowing us to control the ratio of the silane to the bound water. Using this approach, polymeric particles were formed on the surface of cellulose fibers ranging from ∼70 nm to a film. The hydrophobicity of the surface, as determined by water contact angles, correlates with particle sizes (p < 0.001, Student's t-test), and, hence, the hydrophobicity can be tuned (contact angle between 94° and 149°). Using a model structure of a house, we demonstrated that as a result of this modification, paper-based houses can be rendered self-cleaning or tolerant to surface running water. In another application, we demonstrated that the felicitous choice of architectural design allows for the hydrophobic paper to be used for water harvesting.