Forces of interaction between surfaces bearing looped polymer brushes in good solvent

Abstract

In a previous publication we suggested [Huang et al., Macromolecules, 2008, 41, 1745–1752] that looped polymer brushes formed by tethering chains by both ends to a surface may exhibit a polydispersity-like effect due to a distribution of distances between tethering points, leading to segment density profiles dominated by a long and diffuse exponentially-decaying tail. To study this issue in more detail, the force profiles (forces of interaction as a function of separation distance) of a series of looped polymer brushes made by preferential adsorption of poly(2-vinylpyridine)–polystyrene–poly(2-vinylpyridine) (PVP-b-PS-b-PVP) triblock copolymers of varying molecular weight and asymmetry ratio are measured using the surface forces apparatus. The force profiles are analyzed using an equivalent diblock model, which considers the triblock copolymer brushes as being comprised of two diblock copolymers of half the PS molecular weight. While scaling the dependencies of the interaction energy and distance on molecular weight, the tethering density and segment size coalesce the measured force profiles to the “universal profile”, it is necessary to include polydispersity in the description of the equilibrium structure. This is done using the self-consistent field model of Milner et al. [Macromolecules, 1988, 21, 2610–2619]. For looped brushes formed from the symmetric and moderately symmetric triblock copolymers we find that the polydispersity due to molecular weight distribution effectively accounts for the observed force profiles. On the other hand, agreement between the measured and predicted force profiles of looped brushes formed from highly asymmetric copolymers at low degrees-of-compression is achieved only if a much smaller value of the polydispersity index is used in the fitting. The implication of these results is that the shape of the segment density profiles is not due to the previously proposed anchor-induced polydispersity arising due to loop formation; however in the case of highly asymmetric copolymers, loop formation may constrain the stretching of the chains relative to what is expected for brushes formed from the equivalent diblock copolymer.