Tribochemical Reactions Research Articles

Preparation of Diisooctyl Phosphate‐Modified Ultra‐Small Zinc Oxide Nanoparticle and Investigation of Its Tribological Properties as Additive in Alkylnaphthalene

ABSTRACTZnO nanoparticle surface‐modified by diisooctyl phosphate (P204) was prepared by liquid‐phase in situ surface modification technique with zinc acetate as the raw material, P204 as the modifier and anhydrous ethanol as the solvent. The morphology and microstructure of the P204‐ZnO nanoparticle were characterised by transmission electron microscopy, X‐ray diffraction and Fourier transform infrared spectrometry. Its thermal stability was evaluated by thermogravimetric analysis; and its tribological properties as the additive in alkylnaphthalene were evaluated with an SRV‐5 friction and wear tester in reciprocal sliding mode. The results show that the as‐prepared P204‐ZnO nanoparticle has an average particle size of about 4 nm and a P204 content of about 42% (mass fraction); and the surface modifier is grafted onto the surface of ZnO nanoparticle by physical adsorption. With a mass fraction of 0.5% in alkylnaphthalene base oil, P204‐ZnO nano‐additive can mildly reduce the friction coefficient and drastically reduce the wear rate of the steel–steel sliding pair. This is due to the formation of the composite tribofilm via the adsorption and deposition of the nano‐additive on rubbed steel surfaces as well as the tribochemical reactions of the modifier P204 yielding phosphate and of steel substrate yielding iron oxides. The as‐formed composite tribofilm with a thickness of about 20 nm, consisting of phosphate and iron oxides as the binder as well as deposited ZnO nanoparticle as the filling phase, is responsible for the excellent friction‐reducing and antiwear abilities of P204‐ZnO nano‐additive for the steel sliding contact.

Investigation of friction and wear characteristics between modular charge and aluminum alloy for feeding process in artillery systems

In modern artillery systems, frictional properties of modular charge significantly impact the operation of artillery feeding system. In this study, Tribology performance between modular charge and aluminum alloy were investigated under simulated environment of artillery. The result indicates that the COF initially increased and then decreases with the temperature dropped from 50 °C to −40 °C. Additionally, COF increased from 0.19 to 0.41 when relative velocity increased from 100 mm/s to 2000mm/s. SEM detection and chemical composition analysis demonstrated that the main wear forms are adhesive wear and abrasive wear. The tribofilm including aluminum titanium oxide and aluminum nitrides generated through tribochemical reaction, which are beneficial for boundary lubrication. This work provides theoretical reference for artillery tribology research.

Environment-dependent tribochemical reaction and wear mechanisms of Diamond-like carbon: A reactive molecular dynamics study

Diamond-like carbon (DLC) is widely utilized in various fields as a promising solid lubricating material. However, the lubricity and wear behaviors of DLC are highly sensitive to the environment, and the relevant mechanisms are hidden by complex tribochemical reactions at the friction interface. In this study, we performed reactive molecular dynamics (RMD) simulations of DLC to clarify the wear mechanisms in various environments (vacuum, water, and oxygen environments). Two types of tribochemical reaction-induced wear were observed: chemical wear induced by the triboemission of CxHy and CxHyOz compounds and mechanical wear induced by the formation of interfacial C–C bonds. Moreover, the results revealed that the environment affects the tribological behavior of DLC primarily through its impact on the surface chemical state, that is, the quantity and type of surface terminations. In terms of the number of surface terminations, the more surface terminations there are, the more chemical wear and less mechanical wear they cause. In particular, oxygen-containing terminations (e.g., C–OH and C=O) are more resistant than H terminations to interfacial bond formation and mechanical wear. The present work provides important insights into the wear mechanisms of DLC, aiding in the reduction of DLC wear by controlling the environment.

Experimental and numerical investigation of sliding wear of heat-treated 316L stainless steel additively manufactured

Additive manufacturing (AM) of metal alloys using a laser as a machine tool is reaching levels of precision comparable to conventional processing methods. Stainless steel specimens fabricated by AM have been extensively evaluated in load-bearing applications, showing an adequate response concerning mechanical strength. However, research on wear behavior remains open to discussion. The present work evaluates the sliding wear response of 316L stainless steel fabricated by laser powder bed fusion in three conditions: (1) as-built, (2) stress-relieved at 550 °C, and (3) heat-treated at 1150 °C. A pin-on-disk tribometer and a nanoindentation tester were employed to assess the tribological response and compare it with the same cold drawing material. The wear track and volume loss were evaluated using a 3D surface profile meter. Furthermore, the finite element method was applied to validate the experimental results and obtain insights into the behavior of the pin and disk couple. The results show that the samples in the as-built condition exhibit higher wear resistance associated with higher hardness. Stress relief slightly alters the wear response, while heat treatment modifies the microstructure, reducing the sliding wear resistance. The wear of the heat-treated samples cannot be attributed to a single wear mechanism, a synergy between several sub-mechanisms, such as abrasion, adhesion, oxidation, and tribochemical reactions.

Controllable phase transition process of polycrystalline diamond surface for low friction via suppressing oxygen involved tribochemical reactions

The diamond inner wall of drawing die is crucial for the precise formation of ultra-fine wires during the drawing process. Unexpectedly, when drawing soft metal wire, a significant wear occurs on hard-phase diamond surface, resulting in increased friction at the drawing interface, which leads to the wire cross-section distortion, uneven wire diameter, surface scratches and burrs. In this study, the interface interaction and friction products between diamond and iron were investigated, focusing on the primary factors influencing diamond phase transitions by adjusting friction atmosphere. Whether in air or nitrogen, the friction coefficient (CoF) decreases with the increase of load, but CoF value is relatively lower in nitrogen environment. The friction curve of diamond against iron stabilized after an initial downward trend, reaching a minimum CoF of 0.08 in nitrogen under a load of 15 N. The friction mechanism is explained through material transfer, friction products, phase transition, tribolayer formation, and interfaces interactions. It is speculated that in nitrogen, even if a small amount of oxide forms on iron surface, iron remains in contact with diamond, generating a large amount of iron carbide and inducing the graphitization of diamond, which would act as a lubricating role. In contrast, in air, oxygen atoms continuously interact with iron, forming a dense oxide film at the friction interface, which prevents carbon from continuous contacting iron atoms and limits the formation of iron carbide. Overall, the discovery provides new insights into the interaction between metals and diamonds, and offers theoretical guidance for the drawing of iron wires.

Fabrication of ionic liquid-functionalized carbon dots as lubricant additive for friction and wear reduction

Herein, a long-chain ionic liquid with the catecholic group was successfully synthesized and then grafted to the carbon dots surface (CDs-ILs-Br) via the self-assembly capability of catecholic compound. The resulting CDs-ILs-Br exhibit excellent dispersion stability in PEG200, maintaining a uniform dispersion for over one month. With the addition of 3.0 wt% CDs-ILs-Br, the average COF of base oil decreased to 0.113, resulting in 60 % reduction in wear volume. Furthermore, the introduction of anti-wear agent BF4- further reduced average COF to 0.093. XPS and EDS analysis confirm complex tribochemical reactions between CDs-ILs-Br and the friction pair, and the grafting polar molecules of ILs on the carbon dots surface enhanced adhesion effect under high shear condition, forming a robust tribochemical protective film.

Silver with tribo-chemistry facilitation synergized with graphite particles for enhancing the tribo-performance of PEEK composites

The proactive design of tribo-chemistry at friction interface is an effective way to improve the quality of transfer film. Herein, silver served as an assistant in tribo-chemistry, along with graphite incorporated into the short carbon fiber (SCF)/ polytetrafluoroethylene (PTFE)/poly ether ether ketone (PEEK) composite. The lowest wear rate of 3.5 × 10-7 mm3/Nm was achieved for the composite at a graphite content of 5 wt% and a silver content of 5 wt% (Gr5Ag5) under dry friction condition, primarily benefiting from the synergistic interaction of silver and graphite. The transfer of silver and graphite to the friction interface endowed the transfer film with lubricity and load-bearing ability. Crucially, the oxides generated by silver enhanced the strength of the transfer film, and the tribo-chemical reaction involving Ag could increase the bonding of the transfer film to the metal.

Premature Damage in Bearing Steel in Relation with Residual Stresses and Hydrogen Trapping

In this study, premature damage in cylindrical roller bearings made of 100Cr6 (SAE 52100) was investigated. For this purpose, full bearing tests were carried out using two different lubricant formulations with similar viscosities. Published research has pointed out the occurrence of tribo-chemical reactions that cause lubricant degradation and the release of hydrogen in tribo-contact. Hydrogen content measurements were conducted on tested samples, and these measurements showed dependence on the lubricant formulations. Hydrogen diffusion and trapping were identified as significant factors influencing premature damage. The measurement of trapping energies was conducted by thermal desorption spectroscopy, whereas residual stresses, which influence hydrogen diffusion and accumulation, were measured using X-ray diffraction. The measured trapping energies indicated that rolling contact caused the creation and release of hydrogen traps. Over-rolling resulted in changes in residual stress profiles in the materials, demonstrated by changes in stress gradients. These can be directly linked to subsurface hydrogen accumulation. Hence, it was possible to determine that the location of the microstructural damage (WEC) was correlated with the residual stress profiles and the subsurface von Mises stress peaks.

Strengthening mechanism of different morphologies of nano-sized MSH on tribological performance of phosphate/MoS2 bonded solid lubricating coatings

Magnesium silicate hydroxides (MSHs) with granular, schistose, and tubular morphologies were separately incorporated to enhance the tribological properties of phosphate/MoS2 composite coatings. The nano-schistose MSH demonstrated superior tribological performance due to its effective interactions with the worn surface and frictional synergies with solid lubricants. Incorporation of nano-schistose MSH decreased the friction coefficient of composite coatings by about 34.7% and increased the anti-wear performance of composite coatings by about thirteen times. Nano-schistose MSH facilitated the formation of a friction-induced multi-layer heterogenous slipping structure with layered solid lubricants at the friction interface. Moreover, tribo-chemical reactions between nano-schistose MSH and worn surface promoted the in-situ formation of a cermet supporting film, and this also induced the gradual in-situ formation of a lubrication film on the top of worn surface. Consequently, the contact state between tribo-pairs was timely regulated and the invalidation of the nanocomposite slipping structure was effectively restrained during the friction process. As a result, the service life of the phosphate composite coatings was significantly extended and further abrasion on the worn surface was notably reduced.

Dual surface-modification by oleic acid and epoxy-based silane coupling agent providing cerium oxide nanoparticles as additive in pentaerythritol oleate with improved high-temperature adsorption performance and tribological properties

An epoxy-based silane coupling agent (KH560) was grafted onto the surface of oleic acid-modified cerium oxide (CeO2-OA) nanoparticles in order to improve the competitive adsorption ability of the anti-wear additives in ester oils and simultaneously hinder the additive desorption owing to thermal disturbance under high-temperature condition. The as-prepared oleic acid-epoxy silane co-modified cerium oxide (CeO2-OA/E) nanoparticles were characterized. The effect of temperature on the adsorption behavior of trityl phosphate (TCP, a commercial high-temperature antifriction agent), CeO2-OA and CeO2-OA/E in PETO was studied using a dissipative quartz microbalance. Their tribological properties as the additives in pentaerythritol oleate (PETO), a polar ester base oil, were evaluated with a four-ball machine and a ball-on-block friction and wear tester; and their tribomechanism was explored with respect to their adsorption behavior on rubbed steel surfaces at elevated temperatures. It was found that the secondary surface-capping of CeO2-OA by the KH560 silane coupling agent resulted in great increases in the surface potential (from 54 mV to 396 mV) and thermal stability as well (the thermal decomposition temperature rose from 185 °C to 254 °C). Among the tesetd lubricant additives, CeO2-OA/E exhibited the highest adsorption mass, because of the highest surface potential the chemisorption ascribed to the epoxy group of the silane coupling agent. Particularly, CeO2-OA/E added in PETO exhibited better friction reduction and anti-wear properties at 150 °C than CeO2-OA and TCP, because CeO2-OA/E added in PETO formed tribofilm composed of CeO2 and SiO2 with excellent thermal stability as well as friction-reduction and antiwear effects through stable chemical adsorption and tribochemical reaction at elevated temperatures.

Ultra-short running-in period and robust lubricity constructed by dynamic disulfide and hydrogen bonds from ionic liquid polyethylene glycol lubrication

Polyethylene glycol (PEG) system behave the characteristics of non-toxic, non-irritating and good compatibility with various substances, so the improvement and stability of lubrication property and comprehensive performance is vital for PEG system under harsh working conditions. Here, highly reactive ionic liquids (ILs) are designed and introduced with a specifically designed molecular structure, the ultra-short running-in period and robust lubricity can be obtained by dynamic disulfide and hydrogen bonds from the constructed IL-PEG200 lubrication system. Combined with analytical techniques (XPS, FIB-TEM, Nanoindentation, Raman, TOF-SIMS), their interaction was explored to further clarify the interfacial self-assembly behavior. The superior bearing capacity is mainly ascribed to the synergistic effect of carbon-like film, dynamic disulfide bond, hydrogen bonding and interfacial tribochemical reaction.

Tribological properties of YG8/steel friction pair in an aqueous lubrication system with an ionic liquid: Experimental results and molecular dynamics simulations

In this work, an ionic liquid (G-RIC) with excellent lubricating performance was successfully prepared, and the tribological properties as an additive in glycerol-water solutions were explored. The results indicated that 2.0 % additive content can reduced the friction coefficient to below 0.1, leading to a decline in the wear volume of 76 %. Gray cast iron corrosion tests revealed that the additive exhibited excellent corrosion resistance. Quantum chemical calculations revealed that the anion RIC has a low energy gap (ΔE = 0.034 Ha), which implies that it is more prone to undergoing tribochemical reactions with the metal substrate under frictional heat. The synergistic action of the liquid lubrication layer, adsorption film, and friction protective film created an interface that easily shears.

Exploring tribo-electro-chemistry mechanisms of h-BNO@PDA as lubricant additives under electrified conditions for electrical vehicles powertrain

The study explores the use of polydopamine-functionalized hexagonal boron nitride (h-BNO@PDA) as a lubricant/insulator additive in polyalphaolefin (PAO6) oil. This article's novelty lies in the formulation of an innovative lubricant that is free from sulfated ash, phosphorus, and sulfur (SAPS), exhibiting super-lubrication and desirable dielectric properties under electrified conditions. The h-BNO@PDA nanolubricant is specifically designed to mitigate the negative effects of shaft currents and enhance powertrain lubrication for electric vehicles (EVs). Herein, the physicochemical, dielectric strength, and tribological properties of h-BNO@PDA nanolubricant are compared to commercial fully synthetic oil (ATF-6S) used in EVs. The SRV-IV tribometer was used to assess tribological performance under various currents (0–10 A). Subsequently, characterization techniques were utilized to illustrate wear mechanisms and explore tribochemical reactions. The h-BNO@PDA nanolubricant presented superior physicochemical and dielectric properties. The h-BNO@PDA nanolubricant reduced the friction coefficient by 18–20 % and the wear rate by 4–72 % compared to ATF-6S oil under electrified conditions at temperatures of 27 °C and 100 °C. These findings can be attributed to the positive effects of oxidational wear (Fe3O4) and h-BNO@PDA on tribolayer formation under electrification conditions. Eventually, our findings will offer promising insights to enhance the durability of EVs powertrain.

Impact of Relative Humidity on the Formation of Low-Frictional Interface and its Continuity in Tribological Systems with Hydrogenated Carbon Nitride Coatings

The impact of relative humidity on the formation of low-frictional interface in hydrogenated carbon nitride (CNx:H) coatings sliding against Si3N4 balls and the formation continuity was elucidated through friction tests conducted in both air and nitrogen atmospheres with controlled relative humidity levels. In air atmosphere, a carbonaceous tribolayer with a transformed structure from the initial CNx:H was formed on Si3N4 at less than the critical humidity that existed in 1.0–3.0% RH, resulting in low friction (μ < 0.05) and a low specific wear rate of the balls (< 2 × 10–9 mm3/N·m). In contrast, this tribolayer failed to form above 3.0% RH. In nitrogen atmosphere, within the 0.25–1.0% RH range, the tribolayer continued to form concurrently with wear progression, maintaining low friction for over 50,000 cycles. However, in less than this humidity range, the lifetime of low friction was limited owing to the tribolayer’s structural alteration. Thus, relative humidity influences not only the formation of the low-frictional interface but also the formation continuity. On the CNx:H friction surface, hydrogen, hydroxyl, and oxygen groups from environmental water and oxygen molecules continued to chemisorb owing to tribochemical reactions on the uppermost few nanometers during continuous low friction in a nitrogen atmosphere, while hydrogen content of CNx:H desorbed. This study experimentally confirmed the critical role of controlling relative humidity in tribological systems using CNx:H coatings to achieve low friction and improve its durability of low friction through the continuous formation of the low-frictional interface.

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.

Nano-innovations in lubrication: Unveiling the synergistic boundary lubrication potential of zinc titanate with phosphonium ionic liquid

This study investigates the potential of Zinctitanate (ZnTiO3) nanoparticles (APS <100 nm) as nano-additives in lubricant formulations, in conjunction with phosphonium phosphate ionic liquids. Comparative analysis against well-established nano-additives highlights ZnTiO3's exceptional dispersion stability, enduring beyond 225 days. Tribological assessments unveil significant enhancements in antiwear, antifriction, and extreme pressure properties, with 1 wt% ZnTiO3 outperforming the base oil. The ZnTiO3 hybrid nanolubricants exhibited notable synergy, achieving a 49 % reduction in wear compared to hexagonal boron nitride (hBN) and Boehmite NPs. Surface characterization confirms the formation of a protective transfer film (≥100 nm thick), attributed to ZnTiO3's disintegration under tribostress. This results in the development of a mixed metallic metal oxide interfacial film composed of (FeTiO3, FePO4, and ZnO) domains on exposed nascent steel surfaces through tribochemical reactions. These findings suggest ZnTiO3 as a promising nano-additive for advanced lubricants, offering substantial improvements in dispersion stability and tribological performance.

Wear mechanisms of Ni–W and Ni–W/Al2O3 composite coatings sliding against Si3N4 and AISI 52100 steel counterbodies

In this work, wear mechanisms of electrodeposited Ni–W and Ni–W/Al2O3 coatings sliding against Si3N4 and AISI 52100 steel have been comparatively studied. For both Ni–W and its composite coatings sliding against Si3N4, worn morphology shows the tribochemical reaction (tribooxidation) followed by abrasive wear is the dominated mechanism. Comparing with Ni–W coatings, the protective oxide layer is slower peeled off at tribooxidation stage and wear debris are easier squeezed on the Ni–W/Al2O3 during abrasive wear stage. The incorporated Al2O3 provide load bearing effect during microploughing and improve the wear resistance. As sliding against AISI 52100 steel, wear rate of Ni–W/Al2O3 is several times higher than that of Ni–W coatings. Conformity between surfaces of the Ni–W coating and counterbody leads to mild smoothening wear, while the plastic deformation dominated delamination makes severe wear of Ni–W/Al2O3. Deformation resistance of the coatings and transition of counterbodies materials from ceramic to hard metal are responsible for the different wear mechanisms. For Si3N4 ceramic, low thermal conductivity leads to tribooxidation followed by abrasive wear of both Ni–W and Ni–W/Al2O3 coatings. Relatively high deformation resistance of Ni–W coatings is responsible for the conformity as the premise for mild wear sliding against AISI 52100. Low deformation resistance of composite coatings induced by weak interfaces between Al2O3 and Ni–W matrix makes delamination sustained.

Mechanochemical exfoliation of sugar-assisted boron nitride nanosheets for achieving superlubricity and wear distinction

Boron nitride nanosheets (BNNS) possess extensive potential applications across various fields. However, their limited dispersibility in liquids constrains their effectiveness as lubricating additives. In this study, a streamlined sugar-assisted mechanochemical exfoliation technique was employed to concurrently exfoliate and functionalize BNNS. This approach enabled the covalent grafting of sucrose molecules onto BNNS, enhancing their dispersion in water. The application of water containing sucrose-modified BNNS (S-BNNS) facilitated an ultralow coefficient of friction (COF = 0.001) at the Si₃N₄-Si₃N₄ interface. Additionally, using S-BNNS nanosheets as lubricating additives in water achieved superlubricity with a significant surface roughness (Ra ≤120 nm). We explored the correlation between surface roughness and superlubricity, revealing that tribological performance was enhanced by the formation of a tribofilm composed of S-BNNS and a silica layer at the interface through tribochemical reactions. The exceptional anti-wear properties and significantly reduced shear strength of S-BNNS within the tribofilm substantially contributed to achieving the ultralow COF, thus enhancing lubrication performance.

Effect of temperature on the friction behavior and mechanism of DLC film in CO2 foam fracturing environment

Diamond-like carbon (DLC) film is considered to be an attractive candidate material for reducing friction and wear in oil and gas equipment due to its low friction and high wear resistance. This study investigated the evolution of friction interfaces and tribochemical reaction at three different temperatures through reactive molecular dynamics simulations. The results reveal that the synergistic effect of atomic transfer layer and chemical passivation of DLC film leads to the decrease of friction force with increasing ambient temperature. The cumulative atomic transfer layer with increasing ambient temperature also contributes to the increase of wear amount, while the atomic lattice transition dominates friction temperatures. More importantly, the phenomenon of increased sp3 carbon atoms in DLC film is also temperature dependent.

Thermal Stability and High-Temperature Super Low Friction of γ-Fe2O3@SiO2 Nanocomposite Coatings on Steel

The thermal stability of the γ-Fe2O3@SiO2 nanocomposites and super low friction of the γ-Fe2O3@SiO2 nanocomposite coatings in ambient air at high temperature are investigated in this paper. X-ray diffraction, scanning electron microcopy, transmission scanning electron microcopy, high-temperature tribometer, thermogravimetric analysis and differential scanning calorimetry were used to investigate the microstructure, surface morphology and high-temperature tribological properties of the γ-Fe2O3@SiO2 nanocomposite coatings, respectively. The results show that the γ-Fe2O3@SiO2 nanocomposite with the core–shell structure has excellent thermal stability because the SiO2 shell inhibits the phase transition of the γ-Fe2O3 phase to the α-Fe2O3 phase in the nanocomposites. The temperature of the phase transition in γ-Fe2O3 can be increased from 460 to 829 °C. The γ-Fe2O3@SiO2 nanocomposite coatings exhibit super low friction (0.05) at 500 °C. A high-temperature super low friction mechanism is attributed to γ-Fe2O3 and the tribochemical reactions during sliding.