We have investigated the interactions between the positively charged poly[2-(methacryloyloxy)ethyltrimethylammonium chloride] (PMETAC) brushes and the Hofmeister anions and the interactions between the negatively charged poly(3-sulfopropyl methacrylate potassium) (PSPMA) brushes and the Hofmeister cations using a combination of quartz crystal microbalance with dissipation and spectroscopic ellipsometry. A V-shaped anion series is observed in terms of the ion-specific interactions between the PMETAC brushes and the Hofmeister anions. We have found that the chaotropic and kosmotropic anions interact with the PMETAC brushes in different manners. The ion-specific interactions between the PMETAC brushes and the chaotropic anions are dominated by the direct interactions between the anions and the positively charged quaternary ammonium group via ion pairing mediated by ionic hydration strength or polarizability, whereas the ion-specific interactions between the PMETAC brushes and the kosmotropic anions are dominated by the competition for water molecules between the anions and the brushes. The ion-specific interactions between the PMETAC brushes and the anions have significant influences on both the hydration and the conformation of the brushes. The cations exhibit weaker specific ion effects on the PSPMA brushes in comparison with the specific anion effects on the PMETAC brushes.
An ultra-low friction and high load capacity could be obtained on the surfaces grafted by a polymer brush even at relatively slow friction speeds in aqueous lubrication environments, which has attracted widespread attention to study the lubrication mechanism of polymer brushes; however, it has yet to be fully understood. The macroscopic tribological performance of two different polymer brushes, which were prepared by the method of “grafting to” and “grafting from” and named as PLL-g-PEG and PSPMA, respectively, were investigated. The friction results demonstrated that PLL-g-PEG obtained a lower friction coefficient than polymer brush PSPMA, which was ascribed to its unique “self-healing” behavior. The lubrication film was in situ observed and the film thickness induced by the polymer brush was measured using a laboratory set for film thickness measurement apparatus based on interference technology. It was found that PSPMA exhibited excellent lubrication performance not found in PLL-g-PEG, and two film-forming mechanisms highly dependent on velocity were revealed, which may be important to interpret the lubrication mechanism of polymer brushes in aqueous lubricants.Keywords:PLL-g-PEG brushes;PSPMA brushes;friction;film formation property;hydration effect;hydrodynamic effect;lubrication mechanism
危险品化学品经营许可证（带存储）