Carbon Dots with Spatially-Mediated-N/S-Co-Doping Enabling One-Year Stable Lubricant with Oil Leakage Detection Capability.

The dispersion stability of nano-lubricating additives is crucial for the shelf life of lubricant and its practical applications. Nitrogen-sulfur co-doped carbon dots (N,S@CDs) via a one-step hydrothermal method with nitropyrene and thiourea as raw materials are hereby presented. The N and S elements are selectively distributed throughout the entire carbon skeleton with a doping amount of 22.6 at%. The as-synthesized N,S@CDs exhibit excellent dispersion stability in PEG200 and maintain stability for over one year. The experiment results indicate that N,S@CDs significantly improve the anti-wear and friction reduction properties of PEG200, while the friction coefficient is reduced from 0.25 to 0.09 with 1.5 wt% N,S@CDs addition, and the wear volume, depth, and width are reduced by 68%, 52%, and 57%, respectively. The good lubrication performance is attributed to N,S@CDs excellent dispersion stability, enhanced filling and polishing effects, and complex tribochemical reactions caused by heteroatom doping to form a stable protective film on the worn surface. Furthermore, the as-prepared N,S@CDs exhibit intrinsic fluorescence intensity in PEG200 with the photoluminescence quantum yield (PLQY) of 12.5% and remain fluorescent stable during the long-term friction process, therefore the N,S@CDs have a potential application prospect in non-destructive detection of oil leakage via fluorescence labeling method.

Pulsed Laser Manufactured Heteroatom Doped Carbon Dots via Heterocyclic Aromatic Hydrocarbons for Improved Tribology Performance.

Traditional laser-assisted method (top-down synthesis strategy) is applied in the preparation of carbon dots (CDs) by cutting larger carbon materials, which requires harsh conditions, and the size distribution of the CDs is seldom monodisperse. In this work, heteroatom-doped CDs, represented by N,S co-doped CDs (N,S-CDs), can be prepared successfully by pulsed laser irradiation of heterocyclic aromatic hydrocarbons-based small molecule compound solution. The friction coefficient (COF) of base oil PAO decreases from 0.650 to 0.093, and the wear volume reduces by 92.0% accompanied by 1 wt.% N,S-CDs addition, while the load-bearing capacity is improved from 100 to 950 N. The excellent lubrication performance is mainly attributed to the formation of a robust tribofilm via a tribochemical reaction between N,S-CDs and friction pairs, and the N,S-CDs can play a mending effect and polishing effect for worn surfaces. Furthermore, the lubricant containing heteroatom doped CDs are capable of being prepared in situ via pulsed laser irradiation of heterocyclic aromatic hydrocarbons in base oil, which can avoid the redispersed problem of nano-additive in base oil to maintain long-term dispersion, with COF of 0.103 and low wear volume ≈1.99 × 105 µm3 (76.9% reduction) even after standing for 9 months.

Mechanochemical Synthesis of Thiadiazole Functionalized COF as Oil-Based Lubricant Additive for Reducing Friction and Wear.

In this work, the functionalized covalent organic framework (COF) was prepared via a convenient ball milling process. The aldehyde group terminated COF-F reacted with amino thiadiazole in the ball milling jar under mechanical forces; hence, the thiadiazole functionalized COF-F was obtained and denoted as Thdz@COF-F. The as-prepared Thdz@COF-F serves as an oil-based lubricant additive and exhibits remarkable tribological properties, which can reduce the average friction coefficient of base oil from 0.169 to 0.102 and decrease the wear volume by 87.0%. The antifriction and antiwear performances are mainly due to the repairing effect of Thdz@COF-F nanoparticles and the protective tribo-film that averts the direct contact of friction pairs. In addition, through the ball milling method, triazole and thiazole functionalized COF-F were also prepared and represented good lubrication performance, demonstrating the feasibility of this mechanochemical synthesis method for functionalized COFs.

Dynamic Directional Ultrasonically In Situ-Generated N,S-Codoped Carbon Dots in Poly(ethylene glycol) for Improved Tribological Performance.

The dispersion stability of nanomaterials in lubricants significantly influences tribological performance, yet their addition as lubricant additives often presents challenges in secondary dispersion. Here, we present a straightforward method for in situ preparation of N,S-codoped CDs (N,S-CDs)-based lubricants using heterocyclic aromatic hydrocarbons containing N/S elements in poly(ethylene glycol) (PEG) base oil by a directional ultrasound strategy. Two types of N,S-CDs were successfully prepared via the directional ultrasound treatment of PEG with benzothiazole (BTA) and benzothiadiazole (BTH) separately. The resultant N,S-CDs have a uniform distribution of N and S elements and maintain good colloidal dispersion stability in PEG even after 9 months of storage. The N,S-CDs can enter the surface gap of the friction pairs and then induce a tribochemical reaction. Benefiting from the synergistic effect of N and S activating elements, a robust and stable protective film consisting of iron sulfides, iron oxides, carbon nitrides, and amorphous carbonaceous compounds is formed, thus endowing N,S-CDs-based lubricants with improved antiwear and friction-reducing performance. Compared with pure PEG, the coefficient of friction (COF) of the N,S-CDs(BTH)-based lubricant decreased to 0.108 from 0.292, accompanied by a 91.2% reduction in wear volume, and the maximum load carrying capacity increased to 450 from 150 N.