A molecular simulation study of the structure and tribology of polymer brushes: Comparison of behavior in theta and good solvents

Implicit solvent Brownian dynamics simulations of the structure and tribology of opposing polymer-brush covered surfaces have been carried out as a function of surface separation and solvent quality. Consistent with experiment, shear forces were found to be greater under theta solvent conditions than in a good solvent at equal relative separations (normalized by the respective height of the brushes in theta and good solvents). Much higher relative compression is required before the onset of significant shear forces in good solvent compared to theta solvent. The dependence of shear force for a given relative separation on solvent quality can be accounted for by differences in interpenetration of the brushes. When compared as a function of absolute surface separation, greater interpenetration and greater shear force are observed at large separations for the brushes in good solvent than in theta solvent, consistent with the greater brush height in good solvent. At shorter separations, corresponding to moderate to high compression, brush–brush interactions result in significant deformation of the brushes. In this regime, greater interpenetration and greater shear forces are observed in theta solvent at a given separation, in qualitative agreement with experiment.