碳基薄膜水润滑性能的研究进展

评述了碳基薄膜如类金刚石薄膜(DLC)和非晶氮化碳(a-CNx)薄膜水润滑的研究现状和进展。分析了第2元素加入和摩擦副材料对碳基薄膜在水中摩擦磨损特性的影响,探讨了碳基薄膜在水中的磨损机制。指出:氢化或氮化碳基薄膜的磨损率与摩擦副材料的水合反应有关,若摩擦副材料易于摩擦水合反应,碳基薄膜的磨损率很低;3种DLC薄膜在水中的磨损率与DLC的种类和对磨钢球材料无关,都在10-8mm3/(N.m)的数量级上变动;a-CNx/Si基非氧化物陶瓷摩擦副显示很低的摩擦因数和低的磨损率;在相同条件下,a-CNx薄膜比a-C薄膜更能显示优异的水润滑性能。     

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.     

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.     

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 behaviour of hard and superhard coatings at cryogenic temperatures

The work presents data on friction and wear behaviour of pin-on-disc pairs with superhard diamond-like carbon (DLC) coatings and hard coatings of zirconium nitride (ZrN) and titanium nitride (TiN) in liquid nitrogen with loads of 2.5 and 10 N and sliding speed of 0.06 m/s. It is shown that at cryogenic temperatures the friction coefficients of pairs of two types of DLC coatings obtained by vacuum-arc deposition of filtered high-speed carbon plasma fluxes depend to a great deal on the mechanical properties of the coatings defined by predominant sp² or sp³ hybridization of valence electrons. A friction coefficient of 0.76 was observed for friction pairs of superhard (90 GPa) DLC coatings having properties similar to those of diamond. For “softer” DLC coatings of 40 GPa and properties similar to those of graphite the friction coefficient shows lower values (0.24–0.48) dependent on normal load and counterbody material. The DLC coatings obtained by the filtered arc technology exhibit good wear resistance and have strong adhesion to the substrate under friction in liquid nitrogen. With a normal load of 10 N under cryogenic temperature a low wear rate (of the order of 7.2×10⁻⁴ nm/cycle) was found for superhard DLC coatings. The friction coefficient of pairs with hard ZrN and superhard DLC coatings on steel discs was revealed to be linearly dependent on the counterbody material hardness between 20 and 100 GPa. The hardness of the pin was varied by means of depositing TiN or DLC coatings and also by using high-hardness compounds (boron nitride and synthetic diamond). Proceeding this way can be promising since it offers the possibility of creating low-temperature junctions of required friction properties.     

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.     

Wear resistance and anti-sticking properties of duplex treated forming tool steel

The aim of this work was to investigate the potential of using hard physical vapour deposition (PVD) coatings on forming tools, as well as to determine the influence of plasma nitriding on the load-carrying capacity and wear resistance of coated tool surfaces. A load-scanning test rig was used for evaluation, where duplex treated cold work tool steel samples were loaded against soft austenitic stainless steel and hardened ball bearing steel, respectively. Four different coatings (TiN, TiB₂, TaC and DLC) and two substrate treatments (hardening and plasma nitriding in two different gas mixtures) were included.Plasma nitriding alone significantly improved the friction, wear, and anti-sticking properties of the tool steel. PVD coating, and especially PVD coating of nitrided tool steel further improved the performance. Therefore, from the point of view of tool life as well as work peace surface quality, the DLC coating with its excellent anti-sticking properties and sufficiently good wear resistance represent the best solution for forming tool applications of austenitic stainless steel.     

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-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.     

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.     

Tribological Performance of Halogen-Free Ionic Liquids as Lubricants of Hard Coatings and Ceramics

Ionic liquids are expected to be used as new high-performance lubricants because of their low volatility, high thermal stability, and high oxidation stability. It is well known that halogen-containing ionic liquids exhibit excellent lubricity for metals. However, there is a concern about the corrosiveness of ionic liquids caused by the formation of halides. The lubricity of halogen-free ionic liquids for metals is inferior to that of halogen-containing ionic liquids; however, they do not cause any remarkable corrosion effects. In this study, the lubricity of halogen-free ionic liquids—1-butyl-3-methylimidazolium tricyanomethanide ([BMIM] [TCC]) and 1-ethyl-3-methylimidazolium dicyanamide ([EMIM] [DCN])—for hard coatings and ceramics was evaluated using an SRV oscillating sliding tester. Ionic liquids exhibited excellent lubricity for sintered ceramics. It is supposed that the lubricity of ceramics depends on the chemical interaction between the surface and the ionic liquids. Ionic liquids exhibited different lubricating properties with each nitride coating. [EMIM] [DCN] exhibited a better wear reduction than [BMIM] [TCC] on CrN, and its friction coefficient was higher than that of [BMIM] [TCC]. DLC coatings with [EMIM] [DCN] exhibited better lubricity than with [BMIM] [TCC], and the combination of H-free DLC and [EMIM] [DCN] particularly showed excellent lubricity. XPS analysis showed that two kinds of nitrogen compounds were on the sliding surface of H-free DLC lubricated with [EMIM] [DCN].     

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.     

Application of diamond-like carbon coatings to elastomers frictional surfaces

Nitrile-butyl rubber-like materials were coated with amorphous hydrogenated diamond-like carbon (DLC) coatings in order to modify their surface and tribological properties. Measurements of water contact angle were performed by the sessile drop method and showed that the coated samples are more hydrophobic with water contact angles up to 116°. The surface free energy of the elastomers was calculated by the acid-base regression method considering polar and dispersive contributions and the results were correlated with changes in the surface chemistry measured by X-ray photoelectron spectroscopy. It has been found that the lower presence of oxygen functional groups on the elastomer surfaces led to lower surface free energies, even though the polar contribution was not predominant. We also found that the DLC coatings led to a significant decrease of the surface free energy (up to 16%) and that there is a good correlation between the surface free energy values and the corresponding water contact angle values. The coefficient of friction was also measured and presented a significant decrease after coating with DLC.     

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.     

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).     

DLC coating of boundary lubricated components—advantages of coating one of the contact surfaces rather than both or none

The influence of conventional extreme-pressure (EP) and anti-wear (AW) additives on the wear and friction behaviour of DLC coatings has been investigated. Special emphasis was put on exploring if it is most beneficial to coat only one or both the contacting surfaces and on when and how the coatings may improve the friction situation in sliding contact boundary lubricated systems. Tests were performed in a load-scanning test rig, which allows the normal load to gradually increase during the forward stroke and to correspondingly decrease during the reverse stroke. The sliding speed was set to 0.1 m/s, while the normal load was in the range between 140 and 1700 N (2.4–5.6 GPa).This investigation indicates that, under boundary lubrication conditions, addition of commercial AW and EP additives to PAO oil may significantly improve the tribological properties of DLC coatings. Furthermore, the DLC/steel combination was found to give a smoother running-in process and a better tribological performance than the DLC/DLC and steel/steel combination.     

Combination of DLC coatings and EP additives for improved tribological behaviour of boundary lubricated surfaces

The aim of the present investigation was to obtain some further understanding of the mechanism responsible for low-friction behaviour of W-containing DLC coatings (W-DLC) when lubricated with EP additivated oil. Boundary lubricated wear and friction tests were performed under reciprocating sliding motion using a high frequency test rig and a contact pressure of 1.5 GPa. Additionally, some of the tests were performed in a load-scanning reciprocating test rig, with the contact pressure being in the range from 2.4 to 5.6 GPa. The influence of concentration of a sulphur-based EP additive on the friction behaviour was investigated.This investigation showed that W-DLC coatings greatly improve the tribological properties of boundary-lubricated surfaces, especially when pairing coated and uncoated steel surfaces. The improved tribological behaviour was found to be governed by the gradual formation of a WS₂ type tribofilm on the steel counter-face or on revealed steel substrate. The friction level depends on the additive concentration.     

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.     

Improving the performance of a proportional 4/3 water–hydraulic valve by using a diamond-like-carbon coating

Today, there are several water–hydraulic, power-control systems already available on the market. Their components are usually made of stainless steel, which ensures satisfactory performance under mild, conventional operating conditions. However, for more demanding operating conditions and long-term, low-friction and low-wear performance, they do not provide the required performance. One of the possible ways to improve the performance of stainless-steel components in water–hydraulic systems is to coat them with diamond-like carbon (DLC), since this material is well known for its excellent low-friction and low-wear characteristics and also provides very good performance under water-lubrication conditions. In this study, real-scale lifetime tests with 2.3 million cycles were performed on a hydraulic test rig with a proportional 4/3 directional control water–hydraulic valve. Two types of contacts in the valve were tested: the steel-spool/steel-sleeve and the DLC-spool/steel-sleeve. The wear behaviour of the valve was evaluated with a scanning electron microscope (SEM) and internal leakage measurements. In the real-scale lifetime tests the wear and the damage on the DLC-coated spool were significantly lower than on the steel spool. Furthermore, in agreement with this, the internal leakage in the DLC-spool/steel-sleeve valve was almost constant throughout the tests, while in the steel-spool/steel-sleeve valve the leakage slowly, but steadily, increased. The steel/steel and DLC/steel contacts were also separately evaluated in pin-on-disc model tribological tests under water-lubricated conditions for a comparison and for a better understanding of the tribological mechanisms. In agreement with the real-scale tests, the DLC/steel contact showed improved friction and wear performance in comparison with the steel/steel contact.