Critical Packing Density of Water-Mediated Nonstick Self-Assembled Monolayer Coatings

Nanoparticle–mineral surface interactions are relevant in many biological and geological applications. We have previously studied nanoparticle coatings based on closely packed bicomponent polyol–fluoroalkane self-assembled monolayers (SAMs) that can have tunable stickiness on calcite surfaces by changing the compositions of fluoroalkanes in SAMs, where the coatings show nonstick properties if fluoroalkanes can effectively perturb hydration layers on calcite surfaces. However, when applying coatings on nanoparticles, it can be challenging to predict the maximum achievable coating density. Here, we study how would water-mediated SAM–calcite interactions change with different SAM coating densities. Molecular dynamics simulations show that compositionally repulsive, closely packed polyol–fluoroalkane SAMs become adhesive to calcite surfaces with decreasing coating densities. Our modeling shows that this results from the collapsing of fluoroalkanes into the voids of SAMs, where fluoroalkanes can no longer perturb hydration layers on calcite surfaces. Interestingly, we find that the nonstick–stick transition occurs when the volume fractions of the voids on SAMs are greater than the volume fractions of hydrophilic coating molecules.