Durability of ZDDP Tribofilms Formed in DLC/DLC Contacts

The tribological properties of diamond-like carbon (DLC) coatings have drawn much attention of OEMs and lubricant manufacturers in recent years. It is important to know whether conventional friction modifier and antiwear additives can form durable films and work as effectively with DLCs as they normally do on steel surfaces. In this study, the film-forming and friction properties of the antiwear additive ZDDP and the strength of tribofilms formed by this additive on five widely used DLC types, namely a-C:H, a-C:H:W, a-C:H:WC, Si-DLC and ta-C, have been investigated. It is found that ZDDP-derived tribofilms form on all the DLCs but exhibit different friction characteristics based on DLC type. With all DLCs, the amount of tribofilm elements measured after durability tests was less than that measured initially. Over 90 % of thiophosphate and 70 % of sulphide/sulphate were lost during durability tests. ZDDP tribofilms were found to be strongly adhered on Si-DLC and a-C:H compared with the other DLCs. The ZDDP tribofilms formed in DLC/DLC contact appear to be similar in structure to those formed in steel/steel contact but not to exhibit the antiwear performance seen in steel/steel contacts.     

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.     

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.     

The tribological performance of DLC coatings under oil-lubricated fretting conditions

Whether or not the process of fretting occurs is to a large extent dependent on the coefficient of friction, because the coefficient of friction directly affects the amount of shear stress. As a result, the key factor when it comes to reducing the amount of fretting damage is to reduce the coefficient of friction. Various surface coatings, and especially hard, diamond-like carbon (DLC) coatings, are known to be able to produce surfaces with a low level of friction. Despite some such attempts in the past, which did not result in major improvements, the developments and improvements in DLC coatings in recent years suggest the need for a re-evaluation of these coatings for fretting applications. Another way to reduce the amount of friction in mechanical components is to apply lubricants, and recent studies on the lubrication of DLC coatings suggest that this combination could be very successful in preventing failures under boundary-lubrication conditions. Therefore, in this work we present the results of friction and wear measurements from three types of fretting contacts: steel/steel, steel/DLC and DLC/DLC. Boundary oil-lubrication conditions were investigated and a wide range of displacement amplitudes, i.e., from 25 to 500 μm, were selected to assess the fretting and sliding behaviours. The results show a significant difference between the fretting and sliding regimes. In the fretting regime, the DLC-containing contacts, and especially the self-mated DLC/DLC contacts, performed much better than the steel/steel contacts, and significantly reduced both the wear (a 3–10 times reduction with steel/DLC and DLC/DLC) and the friction (a more-than-two-times reduction with DLC/DLC). In the sliding regime, the lubrication effects governed the tribological performance, making the results for all three material combinations very similar.     

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.     

The Effect of Doping Elements and Oil Additives on the Tribological Performance of Boundary-Lubricated DLC/DLC Contacts

In the past decade the range of possible applications for diamond-like carbon (DLC) coatings has changed significantly: from their conventional use in low-stress applications without lubricants, to their use in high-stress applications under lubricated conditions. Despite this progress, there is still a lack of understanding of the lubrication mechanisms involving DLC coatings. Our idea for improving the boundary lubrication of DLC coatings is to dope them with various elements, thus making the coatings more surface-active, in order that they behave in a similar way to conventional metal-lubrication mechanisms. Accordingly, in this paper we present and compare the tribological performance of self-mated (DLC/DLC) non-doped and doped Ti–, W–, and Si–DLC coatings, lubricated with paraffinic mineral oil and using conventional anti-wear (AW) and extreme-pressure (EP) additives. For a comparison, conventional steel/steel contacts were also investigated. The results obtained under relatively severe contact conditions show the significant and beneficial influence of oil additives and DLC doping elements on the wear behaviour. Up to one order of magnitude less wear, as a result of using additives, suggests that efficient boundary lubrication with doped and non-doped DLC coatings can also be achieved and/or improved in self-mated DLC/DLC contacts by using conventional AW and EP additives. The coefficient of friction in DLC contacts increased with the use of additives, but it was always lower than that of steel contacts, thus maintaining the reputation of DLC contacts as low-friction coatings.     

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.     

Lubrication of carbon coatings with MoS2 single sheet formed by MoDTC and ZDDP lubricants

The fuel economy and reduction of harmful elements of lubricants are becoming important issues in the automotive industry. One approach to these requirements is the potential use of low‐friction coatings in engine components exposed to boundary lubrication conditions. Diamond‐like carbon (DLC) coatings, extensively studied as ultra‐low friction films to protect ductile metals surfaces for space applications, are expected to fit the bill. The main purpose of this work is to investigate the friction and wear properties of DLC coatings lubricated with molybdenum dithiocarbamate (MoDTC) and zinc dithiophosphate (ZDDP) under boundary lubrication conditions. The mechanisms by which MoDTC reduces the friction in the centirange were studied using ultra‐high vacuum (UHV) analytical tribometer. The UHV friction tests were performed on a tribofilm previously formed on selected DLC material with MoDTC and ZDDP containing oil. Ex‐situ characterizations show that the composition of this tribofilm is similar to that of a tribofilm obtained on steel surfaces in the same lubrication conditions with MoS₂ single sheets dispersed inside zinc phosphate zones. However, analyses by X‐ray photoelectron spectroscopy (XPS) indicate that MoDTC and ZDDP additives seem to be more active on steel surfaces than carbonaceous ones. After UHV friction with the tribofilm formed on selected DLC and steel pin counterpart, the wear scars of both sliding surfaces were characterized by in‐situ analytical tools such as Auger electron spectroscopy, scanning Auger microscopy and micro‐spot XPS. Low friction is associated with the transfer of a thin MoS₂ film to the steel pin counterpart. Copyright © 2006 John Wiley & Sons, Ltd.     

The Influence of Total Acid Number of Ester Oil in Tribological Behavior of DLC Contacts

The synergetic lubrication effects between diamond-like carbon (DLC) coatings and lubricating oils have draw much attention for the past decades, and promising results have been reported between DLC and biodegradable synthetic ester, which might be a potential solution in energy conservation and environmental protection. However, the challenges lie in that the synthetic ester oils exhibit lower oxidation stability than the hydrocarbon oils and are prone to produce organic acids in the aging process. Thus, investigating the tribological behavior of DLC coating in acidified ester oil is meaningful to the long-term reliability of ester-lubricated DLC contacts. In this article, the friction and wear behavior of DLC–DLC, DLC/steel, and steel–steel contacts in acidic ester oils with different total acid values (TANs) is systematically studied. It was found that acidification of ester oil showed certain beneficial tribological effects for the self-mated steel and DLC contacts but could cause severe wear loss on steel counterparts with a special polished appearance for steel–DLC hybrid contacts. By focusing on the properties of the tribofilm formed on the contact surfaces, a possible tribological mechanism was discussed. Finally, it was proposed that the steel–DLC contacts exhibited low tolerance to organic acids and thus the additives that could dissipate the produced organic acids are a critical component in lubricating oils that were tailored for the steel–DLC contacts.     

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.     

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.     

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.     

Tribological performance of titanium doped and pure DLC coatings combined with a synthetic bio-lubricant

Thermal degradation of environmentally friendly lubricants prevents the spread of its utilisation in industrial applications. This process can be promoted by frictional heating occurred during accidental contacts of moving parts or star-up and shut-down operations. The use of low friction coatings, like diamond-like carbon (DLC), can offer a solution to these problems. Their low friction properties, high wear resistance and excellent corrosion resistance can prevent the occurrence of such local heat spikes, which will protect the lubricant and hence prolong the lifetime of the tribological system. In this work, a synthetic bio-lubricant has been evaluated and compared with a mineral oil. Combinations with pure and Ti doped DLC coatings were taken into account. In order to have a proper evaluation of the tribosystem a wide range of conditions have been considered in high frequency reciprocating and unidirectional tests. The Stribeck curve at variable sliding speeds and loads was obtained. In steel/steel contacts friction is clearly lower when synthetic oil is used compared to a mineral based oil, which is not always true with DLC/DLC contacts. As a result of the tribotesting, the best combination of materials was chosen in order to be validated in a real system (mechanical component in a machine tool), where results confirmed our expectations.     

Non-conventional inverse-Stribeck-curve behaviour and other characteristics of DLC coatings in all lubrication regimes

Due to the specific surface properties of diamond-like-carbon (DLC) coatings their interactions with base oils and additives differ from those of conventional ferrous engineering materials such as steel. This relates not only to their reactions with additives, which were frequently investigated in the past, but also to the effects of base oils and the physical properties of these oils. In order to better understand the physical phenomena of base oils, in this study we analyse the influence of velocity and viscosity (through the Stribeck parameter) on the friction in DLC/DLC contacts for all lubrication regimes. The tribological tests were performed with various non-polar base oils and the behaviour of the DLC/DLC contacts was compared with the steel/steel contacts, where the lubrication mechanisms are well known. Several differences were found for all the lubrication regimes. However, the most surprising is that in the boundary-lubrication regime the Stribeck curve of the DLC contacts has the opposite, i.e., an “inverse”, shape to that of the steel contacts. Namely, the friction of the DLC contacts decreases at low Stribeck-parameter values, rather than showing an increase, as is known from the classical Stribeck-curve theory. This new finding shows that Stribeck curve shape depends strongly on the type of materials in contacts—not only on classical Stribeck parameters (velocity, viscosity, load).     

Comparison of the effects of the lubricant-molecule chain length and the viscosity on the friction and wear of diamond-like-carbon coatings and steel

For steel contacts it is usual for the longer molecular chain lengths of saturated linear hydrocarbons and their acids and alcohols to reduce the coefficient of friction in the boundary-lubrication regime. However, the effect of these lubricant properties on DLC contacts is still unknown. Since the boundary-lubrication mechanisms between DLC coatings and conventional additives do not appear to be as effective as with metals, other potential mechanisms, even though based on weaker interactions or the oil's physical and rheological properties, may thus be very relevant. In this study we focus on the influence of the base oil's chain length and viscosity on the friction and wear in DLC/DLC contacts, and we compare this behaviour with conventional steel/steel contacts, using several simple linear hydrocarbons, i.e., alkanes, and complex branched hydrocarbons, i.e., polyalphaolefins. The results show that in both the steel/steel and DLC/DLC contacts the wear decreases with a longer molecular chain length and a higher viscosity of the oil. However, in DLC/DLC contacts the coefficient of friction increases when oil with a longer molecular chain length or a higher viscosity is used, and decreases with the lower oil viscosity and shorter chain lengths, which is just the opposite to conventional steel/steel behaviour. These results are analysed and discussed in view of lubricant cohesive energy, surface tension, shear strength, viscosity and chain length.     

Tribological behaviour of DLC coatings compared to different materials used in hip joint prostheses

The goal of the study carried out in the laboratory was to quantify the wear and the friction of two materials used for the manufacturing of hip prostheses. Tests used had to obtain in a short time the tribological behaviour laws of the materials. Tests on a hip simulator have been excluded because their cost and their duration were too high for a program of preliminary development of new materials.

To amplify wear phenomena, dry friction tests were carried out for two configurations: ball-on-disc and pin-on-disc. The influence of the contact pressure at constant sliding velocity on the wear of materials has been clearly shown.

Results obtained with several different tested materials (stainless steel/UHMWPE, stainless steel+DLC coating/UHMWPE, stainless steel+DLC coating/stainless steel+DLC coating, titanium alloy+DLC coating/UHMWPE, titanium alloy+DLC coating/titanium alloy+DLC coating, zirconium dioxide/UHMWPE, alumina/UHMWPE, alumina/alumina) have shown the superiority of DLC coatings. Promising results obtained during this study are in the validation stage on a hip simulator.     

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.     

Tribochemistry of silicon and oxygen doped,hydrogenated Diamond-like Carbon in fully-formulated oil against low additive oil

Diamond-like Carbon (DLC) coatings are increasingly used to reduce wear and lower friction in many applications. Doped DLCs are being produced with the goal of further enhancing the friction and wear profile as well as increasing the coating reliability.Silicon is often incorporated into DLC as it is known to affect the sp²/sp³ ratio which in turn can affect the hardness of the film. It can also improve adhesion of the DLC coating to the substrate and lower internal stress.In this study, investigations into the wear behaviour, tribochemistry and oil-formulation dependence of Si, O-doped DLC (Si-DLC) were conducted. The oxidative stability of Si-DLC was also examined.Silicon-doped DLC is able to form a protective tribofilm when a fully-formulated lubricant is used. The tribofilm is composed of S, P, Ca and Zn which are widely recognised as being important to wear reduction.A mechanism of wear repression facilitated by oil additives is proposed.     

Influence of DLC coating thickness on tribological characteristics under sliding rolling contact condition

Diamond-like-carbon (DLC) coating of thickness 3 and 10 μm were developed with and without radical nitriding pretreatment on steel rollers and spur gear pair. The friction coefficient and wear amount were evaluated under sliding rolling contact condition in vacuum and under oil lubrication. Delamination of coatings was observed at the interface of the substrate. The wear resistance of coatings improved with the thickness of the coating. In vacuum both the roller and the gear pair of 10 μm coating thickness with radical nitriding showed identical wear behavior. The radical nitriding seemed to enhance the life of DLC coatings.     

Study of tribological performance of ECR-CVD diamond-like carbon coatings on steel substrates: Part 1. The effect of processing parameters and operating conditions

Diamond-like carbon (DLC) coatings were prepared on AISI 440C steel substrates at room temperature by electron cyclotron resonance chemical vapor deposition (ECR-CVD) process in C₂H₂/Ar plasma. Using the designed Ti/TiN/TiCN/TiC interfacial transition layers, relatively thick DLC coatings (1-2 μm) were successfully prepared on the steel substrates. The friction and wear performance of the DLC coatings was evaluated by ball-on-disk tribometry using a steel counterbody at various normal loads (1-10 N) and sliding speeds (2-15 cm/s). By optimizing the deposition parameters such as negative bias voltage, DLC coatings with hardness up to 30 GPa and friction coefficients lower than 0.15 against the 100Cr6 steel ball could be obtained. The friction coefficient was maintained for 100,000 cycles (∼2.2 km) of dry sliding in ambient environments. In addition, the specific wear rates of the coatings were found to be extremely low (∼10⁻⁸ mm³/Nm); at the same time, the ball wear rates were one order of magnitude lower. The influences of the processing parameters and the sliding conditions were determined, and the frictional behavior of the coatings was discussed. It has been found that higher normal loads or sliding speeds reduced the wear rates of the coatings. Therefore, it is feasible to prepare hard and highly adherent DLC coatings with low friction coefficient and low wear rate on engineering steel substrates by the ECR-CVD process. The excellent tribological performance of DLC coatings enables their industrial applications as wear-resistant solid lubricants on sliding parts.