Interactions between polymer brushes: Varying the number of end-attaching groups

We use a surface force balance (SFB) to study the normal interactions between polymer brushes, which are self-assembled from solution. They consist of polystyrene (PS) chains in toluene (neutral chains in a good solvent) anchored on the interacting mica surfaces via sulfozwitterionic end groups. The properties of the brush depend on the length, N, of the chain, and the energy, αkBT, with which the end group adsorbs on the surface. In contrast to earlier studies where N was varied, we attempt to vary the sticking energy by using polymer chains with one, two, and three zwitterions attached to their ends. We use the theory of Alexander and de Gennes to predict how the normal force profile should vary with α and N, finding, for example, that the brush height L0 obeys L0 = a ·3/5 · α2/5. Surprisingly, our measurements show that the grafting density does not vary significantly between polymers with 1,2, and 3 end groups. This could be attributed to dtpole-dipole interactions between the zwitterions themselves. It is also possible that the effect could be kinetic; that the brush is unable to reach its equilibrium state because successive polymer chains are hindered from attaching to the surface by those already in the brush. Measurements on longer time scales will be necessary to determine whether kinetic effects are important

Effect of end-group sticking energy on the properties of polymer brushes: Comparing experiment and theory

Using surface force balance measurements we have established that polystyrene chains bearing three zwitterionic groups have a higher end-group sticking energy than equivalent chains bearing a single zwitterionic group. In a good solvent, polystyrene chains end-functionalized with three zwitterionic groups form brushes of a higher surface coverage than those bearing a single zwitterion. The increase in surface coverage is slow compared with the initial formation of the brush. Measurements of the refractive index allow us to directly quantify the variation of surface coverage, permitting comparison with models for the kinetics of brush formation based on scaling theory and an analytical self-consistent field. We find qualitative support for associating the kinetic barrier with the energy required for an incoming chain to stretch as it penetrates the existing brush. © 2004 American Institute of Physics

Effect of salt on the compression of polyelectrolyte brushes in a theta solvent

Classical strong-stretching theory (SST) predicts that, as opposing polyelectrolyte brushes are compressed together in a salt-free theta solvent, they contract so as to maintain a finite polymer-free gap, which offers a potential explanation for the ultra-low frictional forces observed in experiments even with the application of large normal forces. However, the SST ignores chain fluctuations, which would tend to close the gap resulting in physical contact and in turn significant friction. In a preceding study, we examined the effect of fluctuations using self-consistent field theory (SCFT) and illustrated that high normal forces can still be applied before the gap is destroyed. We now look at the effect of adding salt. It is found to reduce the long-range interaction between the brushes but has little effect on the short-range part, provided the concentration does not enter the salted-brush regime. Consequently, the maximum normal force between two planar brushes at the point of contact is remarkably unaffected by salt. For the crossed-cylinder geometry commonly used in experiments, however, there is a gradual reduction because in this case the long-range part of the interaction contributes to the maximum normal force