Nanowear studies in chemically heterogeneous responsive polymeric brushes by surface force microscopy

In this study, we present nanowear studies using surface force microscopy (SFM), on nanoscopic thin films of reversibly switchable binary polymer brushes [polystyrene (PS) + poly(2-vinylpyridine) (P2VP)] and respective monobrushes [polystyrene and poly(2-vinylpyridine)] synthesized via “grafting to” method. The aim was to tune the wear in nanothin polymer brush surfaces. Therefore, the effect of conformational switching of PS + P2VP brush on treatment with selective solvents for PS and P2VP chains on the wear process was investigated. Wear process on thick spin-coated films of PS and P2VP was also investigated for comparison. Nanowear experiments were performed using SFM tip by repeating scans over the surface to follow the wear process closely. The wear process on different surfaces was explained on the basis of molecular entanglement as well as adhesion and friction on the sample surface. For spin-coated PS film as well as PS and PS + P2VP brush surfaces (treated with toluene) with molecular entanglements at surface, wear mechanism involved formation of ripples. However, in case of spin-coated P2VP films as well as P2VP and PS + P2VP brush surfaces (treated with ethanol) with no molecular entanglements at surface, wear occurred via removal of polymer chains and their accumulation at the rim. For PS + P2VP surface treated with acidic water, wear mechanism was complex and inhomogeneous ripple formation was followed by formation of heaps of polymeric material in the center of scanned area. The extent of wear as measured either by root mean square roughness of the surface or spacing between the ripples, increased with the number of scans for all the surfaces. Our study shows that wear mode of polymer brush surfaces is different for different polymers and can be controlled/tuned by the use of binary polymer brushes.