Evaporation of Drops Containing Silica Nanoparticles of Varying Hydrophobicities: Exploiting Particle-Particle Interactions for Additive-Free Tunable Deposit Morphology.

We describe the systematic and quantitative investigation of a large number of patterns that emerge after the evaporation of aqueous drops containing fumed silica nanoparticles (NPs) of varying wettabilities for an extended particle concentration range. We show that for a chosen system, the dry pattern morphology is mainly determined by particle-particle interactions (Coulomb repulsion and hydrophobic attraction) in the bulk. These depend on both particle hydrophobicity and particle concentration within the drop. For high and intermediate particle concentrations, interparticle hydrophobic attraction is the dominant factor defining the deposit morphology. With increasing particle hydrophobicity, patterns ranging from rings to domes are observed, arising from the time needed for the drop to gel compared with the total evaporation time. On the contrary, drops of dilute suspensions maintain a finite viscosity during most of the drop lifetime, resulting in dry patterns that are predominantly rings for all particle hydrophobicities. In all investigated systems, the NP concentration corresponded to a large excess of NPs in the bulk compared with the maximal amount that could be adsorbed at available interfaces, making particle-interface interactions such as adsorption of hydrophobic NPs at the air-water interface a negligible contribution over bulk particle-particle interactions. This work emphasizes the advantage of particle surface chemistry in tuning both particle-particle interactions and particle deposition onto solid substrates in a robust manner, without the need for any additive such as a surfactant.