To meet the need for oil-compatible friction modifier additives that can significantly reduce energy consumption in the boundary-lubrication regime, a macromolecular design approach has been taken. The aim was to produce a lubricious polymer film on the sliding surfaces. A series of readily functionalizable block copolymers carrying an oleophilic poly(dodecyl methacrylate) block and a functionalizable poly(pentafluorophenyl methacrylate) block of various lengths was synthesized by means of reversible addition-fragmentation chain-transfer (RAFT) polymerization. The poly(pentafluorophenyl methacrylate) block was used to attach surface-active nitrocatechol anchoring groups to the polymer. The friction-reduction properties of these polymers were assessed with 0.5 wt% solutions in hexadecane by means of rolling-sliding macroscopic tribological tests. Block copolymers with roughly equal block lengths and moderate molecular weights were significantly more effective at friction reduction than all other architectures investigated. They also displayed lower friction coefficients than glycerol monooleate—a commercially used additive. The film-formation ability of these polymers was examined using a quartz-crystal microbalance with dissipation (QCM-D), by monitoring their adsorption onto an iron oxide-coated QCM crystal. The polymer with highest lubrication efficiency formed a thin film of ~ 17 nm thickness on the crystal, indicating the formation of a polymer brush. Interferometric rolling-sliding experiments with the same polymer showed a separating film thickness of ~ 20 nm, which is consistent with the QCM-D value, bearing in mind the compression of the adsorbed layers on the two sliding surfaces during tribological testing.
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