Polymer brushes lead to small friction and wear and thus hold great potential for industrial applications. However, interdigitation of opposing brushes makes them prone to damage. Here we report molecular dynamics simulations revealing that immiscible brush systems can form slick interfaces, in which interdigitation is eliminated and dissipation strongly reduced. We test our findings with friction force microscopy experiments on hydrophilic and hydrophobic brush systems in both symmetric and asymmetric setups. In the symmetric setup both brushes are chemically alike, while the asymmetric system consists of two different brushes that each prefer their own solvent. The trends observed in the experimentally measured force traces and the friction reduction are similar to the simulations and extend to fully immersed contacts. These results reveal that two immiscible brush systems in mechanical contact slide at a fluid-fluid interface while having load-bearing ability. This makes them ideal candidates for tribological applications.
The successful implementation of zwitterionic polymeric brushes as antifouling materials for marine applications is conditioned by the stability of the polymer chain and the brush-anchoring segment in seawater. Here we demonstrate that robust, antifouling, hydrophilic polysulfobetaine-based brushes with diblock architecture can be fabricated by atom-transfer radical polymerization (ATRP) using initiator-modified surfaces. Sequential living-type polymerization of hydrophobic styrene or methyl methacrylate and commercially available hydrophilic sulfobetaine methacrylamide (SBMAm) monomer is employed. Stability enhancement is accomplished by protecting the siloxane anchoring bond of brushes on the substrate, grafted from silicon oxide surfaces. The degradation of unprotected PSBMAm brushes is clearly evident after a 3 month immersion challenge in sterilized artificial seawater. Ellipsometry and atomic force microscopy (AFM) measurements are used to follow changes in coating thickness and surface morphology. Comparative stability results indicate that surface-tethered poly(methyl methacrylate) and polystyrene hydrophobic blocks substantially improve the stability of zwitterionic brushes in an artificial marine environment. In addition, differences between the hydration of zwitterionic brushes in fresh and salt water are discussed to provide a better understanding of hydration and degradation processes with the benefit of improved design of polyzwitterionic coatings.
Poly(N-isopropyl acrylamide) (PNIPAM) is a stimulus-responsive polymer that can switch in water from an expanded state below the lower critical solution temperature (LCST) of 32 °C to a globular state above the LCST. It was recently shown that, as a consequence of this conformational transition, the interfacial and (tribo-)mechanical properties of polymeric systems composed of PNIPAM can be switched between two states. Here we show that the tribo-mechanical properties of a particular type of PNIPAM system, which is the PNIPAM brush, do not just change between two states, but instead evolve continuously and non-monotonically upon increasing/decreasing temperature. To do so, we present atomic force microscopy experiments in which we measure the adhesion hysteresis and the friction upon bringing a gold colloid in relative motion with PNIPAM brushes at temperatures around the LCST. Both the friction and the adhesion hysteresis display a pronounced maximum exactly at the LCST. The force vs. distance data captured at these temperatures show a long-ranged adhesive interaction upon moving the colloid away from the original point of contact, which indicates that during this retraction the partly collapsed polymers in the brush become strongly stretched.
We present a simple method to reversibly switch the adhesive force between two surfaces that are decorated with poly(methyl methacrylate) (PMMA) graft polymers. By employment of a PMMA/isopropanol/water or a PMMA/ethanol/water cosolvent system, we can tune the swelling of the brushes. In pure isopropanol or ethanol the polymer grafts are collapsed, and the adhesion is high when the contacting brushes are pulled apart. In an 80–20 vol % isopropanol–water or ethanol–water composition, the brushes are swollen. In these systems the adhesion is approximately 5 times smaller compared to the adhesion measured in the pure solvent systems. Moreover, we show that PMMA/isopropanol/water cosolvent systems perform better as switchable adhesives than PMMA/ethanol/water cosolvent systems. In the latter pulling events can arise when the swollen brushes are kept in contact for a longer time, such that the adhesion hysteresis can become large and the surface coating can be damaged due to bond-breaking events.
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