Solvent dependent friction force response of polystyrene brushes prepared by surface initiated polymerization

Polystyrene (PS) brushes were prepared on oxide passivated silicon by the surface initiated polymerization (SIP) technique. From an AIBN-type free radical initiator, which was silanized and immobilized on silicon wafers, styrene brushes were directly polymerized and grafted from the surface. The formation of the initiator monolayer and, subsequently, the polymer brush on the surface were monitored by X-ray photoelectron spectroscopy (XPS) and ellipsometry. Friction force measurements were performed by atomic force microscopy (AFM), using a 5 μm SiO ₂ colloidal sphere tip and under systematically varied solvent environments (nonpolar to polar), to demonstrate the dependence of brush lubricity on solvation. The relative uptake of solvents in the PS brush was determined by quartz crystal microbalance (QCM), and it correlates well with friction data. It is surmised that, in poor solvent environments, the polymer brush exists in a collapsed conformation, giving rise to the higher observed friction response.