Surface adsorption of colloidal brushes at good solvents conditions.

Monte Carlo simulations are presented for a minimal model of one spherical colloidal particle as it interacts with one attractive flat substrate. The colloidal particle is decorated by either 6 or 14 grafted polymer chains. The chains are always rather short, with their radius of gyration, estimated at infinite dilution in good solvent conditions, never larger than the spherical colloid diameter. Although all simulations are conducted under "good-solvent" conditions for the grafted polymer chains, we find that small changes in the polymer segment-polymer segment energetic interaction parameter can lead to significantly different scenarios. When the Lennard-Jones attraction is weak, 0.12 k(B)T, increasing the polymer length decreases the likelihood of colloidal adsorption, as expected. On the contrary, when the attraction is 0.18 k(B)T, increasing the length of the grafted polymer chains promotes the adsorption of the colloidal brush onto the surface. When the Lennard-Jones energetic parameter that describes polymer segment-polymer segment interactions is 0.15 k(B)T, as the length of the grafted polymer chains increases the probability of colloidal adsorption decreases to a minimum, and then increases. The results, explained in terms of a competition between entropic (due to the reduction in degrees of freedom available to the grafted polymer chains upon colloidal brush adsorption) and enthalpic driving forces (due to favorable colloid-surface and polymer segment-surface interactions), could be useful for controlling the circulation lifetime of liposomes within the blood stream, and optimizing solar energy harvesting by depositing colloidal particles on solid surfaces.