Surface modification by “polymer
brushes” (dense
end-tethered chains) is a strategy to create a steric barrier against
colloidal aggregation or bioadhesion or to facilitate lubrication.
The approach requires good brush solvation; however, even in a good
solvent, brush chains can adhere certain objects. An important example
is the hydrogen bonding of silica to PEG (poly(ethylene glycol)) chains
in water. To probe how hydrogen bonding at the brush periphery facilitates
adhesive capture of flowing particles, we employ a model system comprising
silica microspheres on biorepellant PEG brushes sufficiently thick
to screen interactions with the underlying substrate. We find that
capture of silica spheres on PEG brushes is slower and less efficient
than the transport-limited rate and can be hindered by the addition
of salt and by flow, up to wall shears at least 500 s–1. Individual flowing silica microparticles adhere gradually to the
PEG brush (presumably by increasing the numbers of H-bonds), so that
the particle motion slows prior to arrest. The deceleration length
is on the order of tens of microns and is salt- and shear-dependent.
By contrast, capture of the same particles on electrostatically attractive
surfaces is transport-limited and occurs when particles “jump”
tens of nanometers to the surface within a fraction of a second rather
than translating near the surface. These distinctly different near-surface
motion signatures may result from fundamental differences in interactions:
PEG–silica hydrogen bonding is short-range and requires registry
of interacting groups, while electrostatic attractions are long-range.
These differences in interactions likely translate to a slower forward
binding constant for hydrogen bonding compared with the diffusion-limited
rate of particle capture in an electrostatically attractive well.
The adhesion of silica particles to a PEG brush comprises a model
for other particles containing H-bond donor surface functionality
(silanols, alcohols, amines) and provides a powerful example of lubrication
versus adhesion at a surface presenting nanoscale deformability.