Behaviour of MoDTC in DLC/DLC and DLC/steel contacts

Diamond-like carbon (DLC) coatings are beginning to be used on machine components parts because of their excellent friction and wear resistance properties. It is hence important to be able to formulate lubricants able to work effectively with these coatings. This requires knowledge of how the various surface-reactive additives generally employed in lubricants behave with DLCs. This paper compares the behaviour of seven types of DLC, a-C, a-C:H, a-C:H:W, a-C:H:WC, Si-DLC, ta-C, ta-C:H, lubricated with molybdenum dialkyldithiocarbamate (MoDTC) solution. It is found that a-C and a-C:H:WC give lower boundary friction than the other types of DLC. MoDTC improves the wear resistance of DLC/DLC contacts but appears to greatly degrade the wear resistance properties of some DLCs in DLC/steel contacts, even though Mo-derived tribofilms form on all DLCs.     

Tribological properties of tribofilms formed from ZDDP in DLC/DLC and DLC/steel contacts

Diamond-like carbon coatings (DLCs) are considered to hold great promise for improvement in friction and wear resistance of engine parts. It is hence interesting to know whether conventional engine oil additives such as ZDDP can form tribofilms and reduce friction and wear in DLC contacts as effectively as they do in steel on steel contacts. This paper compares the behaviour with ZDDP of six different DLC coatings. It is seen that ta-C gives lower boundary friction than the other types while a-C:H gives better wear prevention. A ZDDP-derived tribofilm forms on all DLCs but a pad-like structure is seen only on W-DLC in DLC/DLC tribopairs.     

Non-ferrous coating/lubricant interactions in tribological contacts: Assessment of tribofilms

Use of low friction non-ferrous coatings for engine tribo-components exposed to boundary lubrication is becoming popular in automotive industries. The excellent tribological behaviour of some non-ferrous coatings also reduces dependence on some harmful components of lubricants. In this work, hydrogenated diamond like carbon (HDLC) and chromium nitride (CrN) coatings sliding against cast iron counterbody have been used to study the interaction with friction modifiers (Moly dimer and Moly trimer) and antiwear additive zinc dialkyldithiophosphate (ZDDP) under boundary lubrication condition. The tribological results of the non-ferrous coatings are compared with those of uncoated steel. Tribofilms are formed using a reciprocating pin-on-plate tribometer. The chemical analysis of the tribofilms has been accomplished using X-ray photoelectron spectroscopy (XPS). The XPS analysis shows that the friction modifiers form a low friction tribofilm on the non-ferrous coatings. No antiwear tribofilm derived from ZDDP was observed on the HDLC coating but a stable antiwear tribofilm was found on the CrN coating. Moly dimer together with ZDDP+Base Oil showed the lowest friction coefficient for the CrN coating while Moly trimer along with ZDDP+Base Oil gave the lowest friction for the HDLC coating. This study will investigate the generic differences between the tribofilms formed on the DLC and CrN coatings by two additive-containing oils.     

Reactions of zinc-free anti-wear additives in DLC/DLC and steel/steel contacts

In this work, the ability of ashless anti-wear additives to form protective tribofilms on diamond-like carbon (DLC) and steel surfaces was investigated and compared to the reactions of ZnDTP. Reciprocating sliding tests were performed under mild tribological conditions for steel/steel and DLC/DLC contacts to avoid wearing through the DLC coating. A comparison of the friction behavior of ZnDTP with two ashless additives, a butylated triphenyl phosphorothionate (b-TPPT) and an amine phosphate (AP), indicated that the latter additive behaved in a different manner to the first two. b-TPPT shows the lowest friction coefficient for DLC/DLC contacts whereas the AP give the lowest friction coefficient for steel sliding against steel. AFM and ESEM were performed to analyze the surfaces and showed the build up of tribofilms from ZnDTP and b-TPPT onto both the steel and DLC surfaces. No evidence of such a film formation on DLC was observed when the AP were used.     

Effect of oil additives on the durability of hydrogenated DLC coating under boundary lubrication conditions

Diamond-like carbon (DLC) coatings have became accepted non-ferrous coatings for automotive tribo-components as they offer excellent tribological properties resulting in improved fuel economy and reduced dependence on existing lubricant additives which can be harmful to catalytic converters and ultimately to the environment. Obtaining optimum durability (wear) as well as high fuel economy (low friction) using DLC-coated parts relies in part on the compatibility between surface and lubricant additives. The objective of this study is to understand the role of friction modifiers and antiwear additives on the durability of DLC coating under boundary lubrication conditions. Experiments were performed using a pin-on-plate tribotester using plates coated by 30 at.% hydrogen containing DLC (HDLC) sliding against cast iron (CI) pins. The physical observation of the wear scar, formed on the HDLC coating by low friction and/or antiwear additives, was performed using both optical and scanning electron microscopes. X-ray photoelectron spectroscopy analysis was performed on the tribofilms to help to understand the tribochemical interactions between oil additives and the HDLC coating. Based on the physical observations and tribochemical analysis of the wear scar, the mechanisms of failure/wear of the HDLC coating are proposed and the requirement for designing optimal additive packages for the HDLC coating is discussed.     

Tribochemical interactions of Si-doped DLC film against steel in sliding contact

This study concerns the effects of tribochemical interactions at the interface of Si-DLC (silicon-doped diamond-like carbon) film and steel ball in sliding contact on tribological properties of the film. The Si-DLC film was over-coated on pure DLC coating by radio frequency plasma-assisted chemical vapor deposition (r.f. PACVD) with different Si concentration. Friction tests against steel ball using a reciprocating type tribotester were performed in ambient environment. X-Ray photoelectron spectroscopy (XPS) and auger electron spectroscopy (AES) were used to study the chemical characteristics and elemental composition of the films and mating balls after tests. Results showed a darkgray film consisting of carbon, oxygen and silicon on the worn steel ball surface with different thickness. On the contrary, such film was not observed on the surface of the ball slid against pure DLC coating. The oxidation of Si-DLC surface and steel ball was also found at particular regions of contact area. This demonstrates that tribochemical interactions occurred at the contact area of Si-DLC and steel ball during sliding to form a tribofilm (so called transfer film) on the ball specimen. While the pure DLC coating exhibited high coefficient of friction (∼0.06), the Si-DLC film showed a significant lower coefficient of friction (∼0.022) with the presence of tribofilm on mating ball surface. However, the Si-DLC film possesses a very high wear rate in comparison with the pure DLC. It was found that the tribochemical interactions strongly affected tribological properties of the Si-DLC film in sliding against steel.     

Compatibility of DLC coatings with formulated oils

In the present study, the tribological performance and compatibility of hydrogenated amorphous carbon coating (a-C:H) and metal-doped diamond-like carbon (DLC) coating (Me-C:H) with formulated oils under the boundary lubrication regime was investigated. The investigation employed ball-on-flat contact geometry in reciprocating sliding motion and six formulated oils (manual gearbox oil, automatic gearbox oil, hydraulic oil, compressor oil, and normal and high performance motor oil), with pure poly-alpha-olefin (PAO) oil used as a reference. In addition, DLC coatings behavior in diesel and gasoline fuel was evaluated.Compared with the uncoated steel surfaces a-C:H coatings give improved wear resistance in base PAO as well as in fully formulated oils and fuels. On the other hand, W-doped DLC coatings show the lowest steady-state friction under boundary lubrication, especially when using oils with high additive contents.     

Influence of Silicon on the Wear Properties of Amorphous Carbon Under Dry and Lubricated Conditions

Diamond-like carbon (DLC) coatings have drawn much attention as potential surface coatings for engineering contacts because of their excellent friction and wear resistance properties. However, much less is known about their friction and wear mechanisms, especially at higher contact pressures. In this study, two amorphous carbon DLCs, with (a-C:Si) and without Si (a-C), have been investigated to understand the influence of Si on friction and wear under dry, base oil- and fully formulated oil-lubricated conditions. Si does not affect friction but significantly affects wear. a-C:Si shows lower wear than a-C but imparts higher wear on the steel counterpart. The steel counterpart that forms a hybrid tribolayer (transferred carbon from DLC + additive-derived tribofilm products) exhibits superior wear resistance properties.     

Experimental and Molecular Dynamics Simulations of Tribochemical Reactions with ZDDP: Zinc Phosphate–Iron Oxide Reaction

Zinc phosphate glass is considered to be the main constituent of tribofilms generated under boundary lubrication with zinc dialkyldithiophosphate (ZDDP), a well-known antiwear additive. The reaction occurring during friction between zinc phosphate glasses and steel native iron oxide layer is investigated by both an experimental approach and by Molecular Dynamics simulations (MD). The importance of this “tribochemical” reaction in the general ZDDP antiwear process is discussed.     

Tribological Properties of DLC Coatings in Helium

The aim of this research work was to investigate tribological properties of low-friction DLC coatings when operating in helium atmosphere. Two commercial DLC coatings (a-C:H and Me-C:H) were included in the investigation and compared to reference PTFE-based coatings, normally used on components operating in helium. Coatings were deposited on hardened 100Cr6 bearing steel discs and tested against uncoated steel balls in low-load pin-on-disc contact configuration. Investigation was focused on the effect of substrate roughness (R _a ?=?0.05?C0.2???m) and contact conditions, including contact pressure (150?C350?MPa) and sliding speed (0.2?C0.4?m/s) on the coefficient of friction of DLC coatings operating in helium. Results of this investigation show that for low-load sliding contact DLC coatings provide low friction in helium atmosphere, similar to soft PTFE-based coatings. At the same time DLC coatings investigated were found to substantially reduce wear of the coated surface. However, while the wear of the coated part has been more or less eliminated, application of DLC coating prolongs running-in and increases wear of the steel counter-part. Furthermore, also in helium atmosphere tribolgical behaviour of DLC coatings showed dependence on the coating type and contact conditions.     

Tribological Performance of Halogen-Free Ionic Liquids in Steel–Steel and DLC–DLC Contacts

The tribological performance of halogen-free ionic liquids at steel–steel and diamond-like carbon (DLC)–DLC contacts was investigated. Hydrogenated amorphous carbon (a-C:H) and tetrahedral amorphous carbon (ta-C) were used as test specimens. Friction tests were carried out on steel–steel, a-C:H–a-C:H, and ta-C–ta-C contacts by using a reciprocating cylinder-on-disk tribotester lubricated with two different types of halogen-free ionic liquids: 1-ethyl-3-methylimidazolium dicyanamide ([BMIM][DCN]) and 1-butyl-3-methylimidazolium tricyanomethanide ([BMIM][TCC]). From the results of friction tests, the ta-C–ta-C tribopair lubricated with [BMIM][DCN] or [BMIM][TCC] exhibited an ultralow friction coefficient of 0.018–0.03. On the other hand, ultralow friction was not observed at the steel–steel and a-C:H–a-C:H contacts. Measurements obtained with a laser scanning microscope and an atomic force microscope (AFM) showed that a chemical reaction film, derived from the ionic liquid lubricant used, was formed on the steel surfaces. However, this chemical reaction film was not observed on either of the DLC surfaces. The AFM results showed that there were high-viscosity products on the ta-C surfaces, that the wear tracks on the ta-C surfaces exhibited low frictional properties, and that the ta-C surfaces were extremely smooth after the friction tests. Based on these results, it was concluded that an ionic liquid–derived adsorbed film formed on the ta-C surface and resulted in the ultralow friction when lubricated with a halogen-free ionic liquid.     

Tribological behavior and tribofilm composition in lubricated systems containing surface-capped molybdenum sulfide nanoparticles

The tribological behavior of surface-capped MoS₃ nanoparticles (nano-MoS₃) in hydrocarbon oils was studied both alone and in combination with ZDDP. It was found that the nano-MoS₃ additive alone demonstrates pro-wear properties and decreases the friction coefficient only at high temperatures. The combination with ZDDP demonstrates synergism in antiwear and antifriction activity even at low ZDDP content. X-ray Absorption Near Edge Structure (XANES) spectroscopy at the sulfur, molybdenum and phosphorus edges was used to identify the chemical species in tribochemical films. It was established that the nano-MoS₃-formed tribofilms are composed of oxidized sulfur and molybdenum species while tribofilms formed by combination with ZDDP are composed of phosphate layers incorporating MoS₂-type fragments providing friction reduction.     

Characterization of tribofilms derived from zinc dialkyl dithiophosphate and serpentine by X-ray absorption spectroscopy

The tribological performance of serpentine in combination with ZDDP as additive for base oil was investigated by a Plint high frequency friction tester at room temperature and 100 °C. The tribofilms formed by serpentine and ZDDP were analyzed using the scanning electron microscopy technique equipped with energy dispersive X-ray spectroscopy. X-ray absorption spectroscopy at phosphorus K- and L_3,2-edges, sulfur K- and L_3,2-edges, silicon K-edge, magnesium K-edge, oxygen K-edge, and zinc L_3,2-edge were recorded to determine the chemistry of the tribofilms. It is found that a combination of serpentine with ZDDP helps reduce the friction of oil blend and exhibits better antiwear properties than base oil.     

Molecular dynamics simulations of atomic-scale tribology between amorphous DLC and Si-DLC films

Silicon-doped diamond-like carbon (Si-DLC) films possess the potential to improve wear performance of DLC films in humid atmospheres and at higher temperatures. But many experimental results of Si-DLC films show that their structures and tribological properties changed greatly with silicon content. Therefore, molecular dynamics (MD) simulations were used to study the sliding friction process between DLC and Si-DLC films on un-lubricated boundary condition. The results show that a part of sp² bonding of the Si-DLC films is converted into sp³ bonding with the addition of silicon atoms, and the sp³/sp² ratio increases with the increase in silicon content. A transfer film between the DLC and Si-DLC films is formed and the friction force changes with the silicon content. Moreover, the simulations have showed that the silicon addition promotes the bonding of interfilms being formed.     

Boundary lubrication mechanisms of carbon coatings by MoDTC and ZDDP additives

Fuel economy and reduction of harmful elements in lubricants are becoming important issues in the automotive industry. An approach to respond to these requirements is the potential use of low friction coatings in engine components exposed to boundary lubrication conditions. Diamond-like-carbon (DLC) coatings present a wide range of tribological behavior, including friction coefficients in ultra-high vacuum below 0.02. The engine oil environment which provides similar favourable air free conditions might lead to such low friction levels.In this work, the friction and wear properties of DLC coatings in boundary lubrication conditions have been investigated as a function of the hydrogen content in the carbon coating. Their interaction with ZDDP which is the exclusive antiwear agent in most automotive lubrication blends and friction-modifier additive MoDTC has been studied. Hydrogenated DLC coatings can be better lubricated in the presence of the friction-modifier additive MoDTC through the formation of MoS₂ solid lubricant material than can non-hydrogenated DLC. In contrast, the antiwear additive ZDDP does not significantly affect the wear behavior of DLC coatings. The good tribological performances of the DLC coatings suggest that they can contribute to reduce friction and wear in the engine, and so permit the significant decrease of additive concentration.     

A comparison of the tribological behaviour of steel/steel, steel/DLC and DLC/DLC contacts when lubricated with mineral and biodegradable oils

Diamond-like carbon (DLC) coatings, which can nowadays be applied to many highly loaded mechanical components, sometimes need to operate under lubricated conditions. It is reasonable to expect that in steel/DLC contacts, at least the steel counter body will behave according to conventional lubrication mechanisms and will interact with lubricants and additives in the contact. However, in DLC/DLC contacts, such mechanisms are still unclear. For example, the “inertness” of DLC coatings raises several questions about whether they are able to provide real boundary “lubrication” or whether they are just a “passive” member in these contacts. On the other hand, biodegradable oils, in particular vegetable base oils, possess a good lubricating ability, often much better than mineral or conventional synthetic oils as a result of the large amount of un-saturated and polar components that can promote the lubricity of DLC coatings. Accordingly, in this study, we present the results of experiments under severe boundary-lubrication conditions during reciprocating sliding. We look at the effect of the type of mating surfaces - steel/DLC, DLC/DLC and steel/steel - and the type of oil on the tribological performance of DLC coatings. We compare the wear and friction behaviours of two types of DLC coatings, i.e., a “pure” non-doped a-C:H DLC coating (denoted as a-DLC) and a WC-containing multilayer coating (denoted as W-DLC) tested with a mineral oil and a biodegradable vegetable oil. These oils, which have very different chemical compositions, were used as base oils and also with mild AW and strong EP additives. Among other things, the results confirm the following: (1) coating/coating lubricated contacts can resemble metal-lubrication mechanisms; (2) additives reduce wear in coating/coating contacts by up to 80%; (3) better wear and friction performance are obtained with oils that contain large amounts of polar and un-saturated molecules; (4) a coating/coating combination generally results in less wear than a steel/coating combination.     

Friction and wear behavior of diamond-like carbon coating on plasma nitrided mild steel under boundary lubrication

The friction and wear properties of synthetic ionic liquid functionalized borate esters as additives in poly-alpha-olefin (PAO) were measured for diamond-like carbon (DLC) coating on plasma nitrided AISI 1045 steel. Results show that the borate esters gave much better friction–reduction and antiwear properties for DLC coating/steel and DLC coating/DLC coating sliding pairs than zinc dialkyldithiophosphate (ZDDP). In addition the DLC coating had much better wear resistance than the nitrided mild steel substrate, indicating that duplicate surface modification was more effective in significantly increasing the wear resistance of mild steel.     

Effects of sliding velocity and normal load on friction and wear characteristics of multi-layered diamond-like carbon (DLC) coating prepared by reactive sputtering

Friction and wear tests were performed to investigate effects of sliding velocity and normal load on tribological characteristics of a multi-layered diamond-like carbon (DLC) coating for machine elements. The DLC coatings which consist of sequentially deposited gradient Cr/CrN, W-doped DLC (a-C:H:W) and DLC (a-C:H) layers were formed on carburized SCM 415 Cr–Mo steel disks using a reactive sputtering system. The tests against AISI 52100 steel balls were performed under various sliding velocities (0.0625, 0.125, 0.25, 0.5, 1 and 2 m/s) and normal loads (6.1, 20.7 and 49.0 N) in ambient air (relative humidity=26±2%, temperature=18±2 °C). Each test was conducted for 20 km sliding distance without lubricating oil. The results show that friction coefficients decrease with the increase in sliding velocity and normal load. Wear rates of both surfaces decrease with the increase in normal load. The increase in sliding velocity leads initially to the increase in wear rates up to the maximum value. Then, they decrease, as the sliding velocity increases above specific value that corresponds to the maximum wear rate. Through surface observation and analysis, it is confirmed that formation of transfer layers and graphitized degree of wear surfaces of DLC coatings mainly affect its tribological characteristics.     

Friction Reduction and Antiwear Capacity of Engine Oil Blends Containing Zinc Dialkyl Dithiophosphate and Molybdenum-Complex Additives

The efficacy of oil blends containing zinc dialkyl dithiophosphate (ZnDTP) and molybdenum (Mo)-complex additives to improve the tribological properties of boundary-lubricated steel surfaces was investigated experimentally. The performance of oil blends containing three different types of Mo-complex additives of varying Mo and S contents with or without primary/secondary ZnDTP additions were investigated at 100°C. The formation of antiwear tribofilms was detected in situ by observing the friction force and contact voltage responses. Wear volume and surface topography measurements obtained from surface profilometry and scanning electron microscopy studies were used to quantify the antiwear capacity of the formed tribofilms. The tribological properties are interpreted in terms of the tribofilm chemical composition studied by X-ray photoelectron spectroscopy. The results demonstrate that blending the base oil only with the Mo-compound additives did not improve the friction characteristics. However, an optimum mixture of Mo complexes and ZnDTP additive provided sufficient amounts of S and Mo for the formation of antiwear tribofilms containing low-shear strength MoS ₂ that reduces sliding friction. In addition, the formation of a glassy phosphate phase due to the synergistic effect of the ZnDTP additive enhances the wear resistance of the tribofilm. This study shows that ZnDTP- and Mo-containing additives incorporated in oil blends at optimum proportions improve significantly the tribological properties of boundary-lubricated steel surfaces sliding at elevated temperatures.     

Super low friction of DLC applied to engine cam follower lubricated with ester-containing oil

This paper presents a material combination that reduces the friction coefficient markedly to a superlow friction regime (below 0.01) under boundary lubrication. A state approaching superlubricity was obtained by sliding hardened steel pins on a hydrogen-free diamond-like carbon (DLC) film (ta-C) lubricated with a poly-alpha-olefin (PAO) oil containing 1 mass% of an ester additive. This ta-C/steel material combination showed a superlow friction coefficient of 0.006 at a sliding speed of 0.1 m/s. A hydrogencontaining DLC coating/steel combination also showed a lower friction coefficient in air than a steel/steel combination, 0.1 vs. 0.8, but no large reduction was observed when the sliding surfaces were lubricated with ordinary 5W-30 engine oil and the PAO oil containing an ester additive. The friction coefficient of the hydrogen containing DLC/steel combination lubricated with the PAO containing an ester additive was above 0.05. On the other hand, the superlow friction performance demonstrates that the rolling contact friction level of needle roller bearings can be obtained in sliding contact under a boundary lubrication condition. It is planned to apply this advanced DLC coating technology to valve lifters lubricated with a newly formulated engine oil in actual mass-produced gasoline engines. A larger friction reduction of more than 45% is expected to be obtained at an engine speed of 2000 rpm.