Nanoscale Contact Mechanics between Two Grafted Polyelectrolyte Surfaces

The adhesive and frictional behavior of end-grafted poly­[2-(dimethyl­amino)­ethyl methacrylate] (PDMAEMA) films (brushes) in contact with atomic force microscope tips from which PDMAEMA or poly­(methacrylic acid) (PMAA) were grafted has been shown to be a strong function of pH in aqueous solution. The interaction between the brush-coated surfaces is determined by a combination of electrostatic and noncovalent interactions, modulated by the effect of the solvation state on the brush and the resulting area of contact between the probe and the surface. For cationic PDMAEMA–PDMAEMA contacts at low pH, the brushes are highly solvated; a combination of electrostatic repulsion and a high degree of solvation (leading to a significant osmotic pressure) leads to a small area of contact, weak adhesion, and energy dissipation through plowing. As the pH increases, the electrostatic repulsion and the osmotic pressure decrease, leading to an increase in the area of contact and a concomitant increase in the strength of adhesion through hydrophobic interactions; as a consequence, the friction–load relationship becomes nonlinear as shear processes contribute to friction and the mechanics are fitted by DMT theory and, at higher pH, by the JKR model. For PDMAEMA–PMAA, the electrostatic interaction is attractive at neutral pH, leading to a large adhesion force, a large area of contact, and a nonlinear friction–load relationship. However, as the pH becomes either very small or very large, a significant charge is acquired by one of the contacting surfaces, leading to a large amount of bound solvent and a significant osmotic pressure that resists deformation. As a consequence, the area of contact is small, adhesion forces are reduced, and the friction–load relationship is linear, with energy dissipation dominated by molecular plowing