Interfacial activity of polymer-coated gold nanoparticles

A systematic study of the interfacial activity of polymer-coated gold nanoparticles was performed with the use of a computer-controlled four-roll mill. The nanoparticle locality within the polymeric domains (bulk or interface) was controlled by means of a mixture of polymeric ligands grafted to the gold nanoparticle core. The bulk polymers were polybutadiene (PBd) and polydimethylsiloxane (PDMS). Monoterminated PDMS and PBd ligands were synthesized on the basis of the esterification of reactive groups (such as hydroxyl or amino groups) with lipoic acid anhydride. The formation of polymer-coated nanoparticles using these lipoic acid-functionalized polymers was confirmed via transmission electron microscopy (TEM), and their interfacial activity was manifested as a reduction of the interfacial tension and in the enhanced stability of thin films (as seen via the inhibition of coalescence). The nanoparticles showed an equal, if not superior, ability to reduce the interfacial tension when compared to previous studies on the effect of insoluble surfactants; however, these particles proved not to be as effective at inhibiting coalescence as their surfactant counterpart. We suggest that this effect may be caused by an increase in the attractive van der Waals forces created by the presence of metal-core nanoparticles. Experimental measurements using the four-roll mill allow us to explore the relationship between nanoparticle concentration at the interface and interfacial tension. In particular, we have found evidence that the interface concentration can be increased relative to the equilibrium value achieved by diffusion alone, and thus the interfacial tension can be systematically reduced if the interfacial area is increased temporarily via drop deformation or breakup followed by recoalescence.