Integration of Functionalized Polyelectrolytes onto Carbon Dots for Synergistically Improving the Tribological Properties of Polyethylene Glycol

In this work, we carefully designed and synthesized a series of novel polyelectrolyte-functionalized carbon dots (CDs-PEI-X) by a facile and reversible phase transfer method based on the protonation reaction and anion exchange process executed on the surface of polyethylenimine-grafted CDs (CDs-PEI), where X denotes the anionic moieties of polyelectrolyte shells including hexafluorophosphate (PF₆^–), bis­(trifluoromethane)­sulfonimide (NTf₂^–), oleate (OL^–), and bis­(salicylato)­borate (BScB^–), respectively. Attributed to the favorable compatibility of these anions and polyethylene glycol (PEG) molecules, the hydrophobic CDs-PEI-X displayed excellent dispersibility and long-term stability in PEG200 base oil. Subsequently, the tribological behaviors of CDs-PEI-X as the lubricant additives of PEG200 were systematically investigated. It was proved that the anionic moieties of the polyelectrolyte shells of CDs-PEI-X played a crucial role in regulating their tribological behaviors. Particularly, CDs-PEI-OL was confirmed as an optimal additive, exhibiting the best lubricity, outstanding load-bearing capacity, long service life, and remarkable operational stability under boundary lubrication regime. Based on the tribological evaluations and worn surface analyses, the lubrication mechanism of CDs-PEI-OL was mainly attributed to the formation of the organic–inorganic hybrid adsorption film, the protective tribofilm, and its nanolubrication functions as scrollable “ball-bearing”, i.e., the synergistic lubrication effects of surface polyelectrolyte shells and carbon cores. This study provides a feasible and versatile strategy to rapidly and effectively tailor the surface chemistry of CDs and discloses the essential contribution of carbon cores and surface groups on the lubrication process, which facilitates the development of advanced CDs-based nanolubricant additives.