Synergistic Tribo-Activity of Nanohybrids of Zirconia/Cerium-Doped Zirconia Nanoparticles with Nano Lamellar Reduced Graphene Oxide and Molybdenum Disulfide

Zirconia and 10%, 20%, and 30% cerium-doped zirconia nanoparticles (ZCO), ZCO-1, ZCO-2, and ZCO-3, respectively, were prepared using auto-combustion method. Binary nanohybrids, ZrO₂@rGO and ZCO-2@rGO (rGO = reduced graphene oxide), and ternary nanohybrids, ZrO₂@rGO@MoS₂ and ZCO-2@rGO@MoS_2, have been prepared with an anticipation of a fruitful synergic effect of rGO, MoS₂, and cerium-doped zirconia on the tribo-activity. Tribo-activity of these additives in paraffin oil (PO) has been assessed by a four-ball lubricant tester at the optimized concentration, 0.125% w/v. The tribo-performance follows the order: ZCO-2@rGO@MoS₂ > ZrO₂@rGO@MoS₂ > ZCO-2@rGO > ZrO₂@rGO > MoS₂ > ZrO₂ > rGO > PO. The nanoparticles acting as spacers control restacking of the nanosheets provided structural augmentation while nanosheets, in turn, prevent agglomeration of the nanoparticles. Doped nanoparticles upgraded the activity by forming defects. Thus, the results acknowledge the synergic effect of cerium-doped zirconia and lamellar nanosheets of rGO and MoS₂. There is noncovalent interaction among all the individuals. Analysis of the morphological features of wear-track carried out by scanning electron microscopy (SEM) and atomic force microscopy (AFM) in PO and its formulations with various additives is consistent with the above sequence. The energy dispersive X-ray (EDX) spectrum of ZCO-2@rGO@MoS₂ indicates the existence of zirconium, cerium, molybdenum, and sulfur on the wear-track, confirming, thereby, the active role played by these elements during tribofilm formation. The X-ray photoelectron spectroscopy (XPS) studies of worn surface reveal that the tribofilm is made up of rGO, zirconia, ceria, and MoS₂ along with Fe₂O₃, MoO₃, and SO₄^2- as the outcome of the tribo-chemical reaction.