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.     

ZDDP and MoDTC interactions in boundary lubrication—The effect of temperature and ZDDP/MoDTC ratio

Tribofilms formed under boundary lubrication from ZDDP and MoDTC additives alone or in different ratios in the lubricant have been studied. The tribological performance is linked to the tribofilm properties and consequently to the lubricating conditions. Tribofilms are formed using a reciprocating pin-on-plate tribometer. Surface sensitive analytical techniques, such as energy dispersive X-ray analysis (EDX) and X-ray photoelectron spectroscopy (XPS) have been used for tribofilm characterisation. The XPS peaks have been deconvoluted to characterise the species formed in the wear scar. The formation of species with different tribological properties, due to the decomposition of ZDDP and MoDTC molecules as a result of testing temperature, is shown. Surface analyses have shown that MoDTC decomposes, even in low-lubricant bulk temperature tests (30 °C), forming the same species as in high-lubricant bulk temperature tests (100 and 150 °C) but the tribofilms give different tribological performance. The effectiveness in friction reduction is shown to depend on the ratio between what are defined as high- and low-friction species in the tribofilm.     

XPS and XANES characteristics of tribofilms and thermal films generated by two P- and/or S-containing additives in water-based lubricant

Two phosphates were synthesized and their tribological properties as water-soluble lubricant additives were evaluated by using four-ball tester. The micro/nano-scale chemical characteristics of tribofilms and thermal films formed from these additives in different conditions were explored by X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES) spectroscopy. The results show that the additives have better anti-wear and friction reducing properties than the oleate solution at higher load. Surface analysis results indicate that tribofilms are mainly composed of absorbed layer and chemical reactant layer, in which phosphorus exists in the form of adsorbed molecule, phosphate or polyphosphate, and sulfur in the form of alkyldisulfide, sulfide and sulfate. As to the thermal films, phosphate (or polyphosphate) and sulfate are detected as the main components. The anti-wear and friction-reducing performances can be ascribed to the formation of films on the metal surface, and the mechanism of the process of molecules adsorption, new compounds production through tribochemical reactions, film formation and destruction.     

Tribological characteristics of ashless dithiocarbamate derivatives and their combinations with ZDDP as additives in mineral oil

Two ashless dithiocarbamate derivatives, octyl 2-(dibutylcarmothioylthio) acetate (DDCO) and S-dodecyl 2-(dibutylcarbamothioylthio) ethanthioate (DDCS), were prepared. Thermal stabilities tests were conducted with a thermo-gravimetric analyzer (TGA). The tribological properties of each compound and their combinations with ZDDP in a mineral oil (HVI WH150) were evaluated using a four-ball tester. X-ray absorption near-edge structure (XANES) spectroscopy was used to characterize the chemical properties of tribofilms generated from DDCO, DDCS and their combinations with ZDDP. According to the TGA results, the synthesized compounds possess good thermal stability (initial decomposition temperatures are above 270 °C). It can be found that all the prepared compounds have better friction-reducing capacity than ZDDP, with anti-wear performance and extreme pressure property worse than ZDDP. However, their combinations with ZDDP perform better than ZDDP in tribological properties. The results of the XANES analyses indicate that the composition of the tribofilms from DDCO or DDCS is organic sulphide on the outer surface and pyrite with a little sulphite in the inner layer, which also suggests the -SC(=S)-N- part in additives structure plays key role in tribol-chemical behaviour. The XANES spectra of the combinations exhibit interestingly that the addition of DDCO or DDCS can increase the length of polyphosphate chain in the tribofilms.     

Structural, mechanical and tribological investigations of sputter deposited CrN-WS2 nanocomposite solid lubricant coatings

Nanocomposite coatings of CrN-WS₂ were prepared at different Cr contents (approximately 8-39 at%) using an unbalanced magnetron sputtering system. Structural changes in CrN-WS₂ coatings with variation in Cr content were studied using X-ray diffraction. CrN-WS₂ coatings displayed a dense, compact microstructure with reduced columnar growth in the field emission scanning electron microscopy data. Nanoindentation and nanoscratch data showed that CrN-WS₂ coatings exhibited improved mechanical and adhesive properties, respectively. Micro-tribometer tests at a load of 2 N indicated that CrN-WS₂ coatings prepared at 31 at% Cr exhibited a stable friction coefficient of 0.20-0.24 even after 8 h.     

A comparative study on the evaluation of the tribological behaviour of polymer/zinc coated steel sheets

A major factor affecting the formability of coated automative steel sheets is the interfacial frictional behaviour between the sheet and the forming die. Within this study, the suitability of standard laboratory-type tribological tests (pin-on-disc and block-on-cylinder test) to evaluate the tribological behaviour of uncoated and zinc and zinc/polymer coated steel sheets in dry sliding contact with cold working steel is investigated. The results obtained are compared to those obtained by a deep drawing experiment. Friction coefficients measured during the running-in stage of the pin-on-disc test seem to be well suited to distinguish between the different frictional behaviour of coated steel sheets.     

Improvement of tribological performance of steel by solid lubricant shot-peening in dry rolling/sliding contact wear tests

The effect of shot-peening treatment with the particulate MoS₂ solid lubricant on the wear resistance of steel in the dry rolling/sliding contact wear tests was investigated. The duplex shot-peening treatment with ceramic balls and the particulate MoS₂ solid lubricant provided excellent wear resistance under a severe loading and sliding condition because the uniform and minute surface roughness given by shot-peening treatment with ceramic balls could keep shot-peened MoS₂ particles with a low friction coefficient on the sample surface. Furthermore, the sample surface was covered with shot-peened MoS₂ particles by a MoS₂ layer formed during the rolling/sliding contact wear test.     

Structure and water-lubricated tribological properties of Cr/a-C coatings with different Cr contents

The Cr containing amorphous carbon coatings (Cr/a-C) with varying Cr content were deposited using unbalanced magnetron sputtering. The results revealed that the chromium carbide nano-clusters were formed when the Cr content exceeded 4.9 at%. The critical load increased while the hardness decreased after the Cr element incorporation. Although the low Cr containing Cr/a-C coatings (≤4.9 at%) exhibited similar friction coefficient with a-C coatings, but the initial friction coefficient, running-in distance and wear rate of SUS440C balls all decreased. However, the Cr/a-C coatings with high Cr content (11.98–14.09 at%) would worsen the tribological properties because chromium carbides acted as abrasive wear particles during tribotests.     

Assessment of the factors influencing micropitting in rolling/sliding contacts

Micropitting is currently a significant failure mechanism in carburised steel gears, but the detailed mechanisms of crack initiation and propagation are not well understood. Experiments have been carried out using a twin disc machine, according to a factorial experimental design in order to assess the influence of seven factors: material, surface finish, lubricant, load, temperature, speed and, slide-to-roll ratio. In order to minimise time, the design adopted was a fractional factorial design 2^(7-4). It has been found that load has the biggest effect on micropitting initiation whereas speed and slide-to-roll ratio have the biggest effects on micropitting propagation. Finally it is shown that micropitting is related to the phenomenon of martensite decay.     

Effect of shot peening on rolling contact fatigue and lubricant film thickness within mixed lubricated non-conformal rolling/sliding contacts

The effect of shot peening on rolling contact fatigue (RCF) and lubricant film thickness within non-conformal rolling/sliding contacts operated under mixed lubrication conditions was observed in this study. Rolling contact fatigue tests and film thickness measurements were carried out using specimens with modified surface topography by shot peening process using glass beads having diameter between 0.07 and 0.11 mm. It has been shown that the effect of shot peening on RCF has no positive effect even if shot peened surface of the roller exhibited somewhat higher hardness in contrast to the grounded surface. The reduction of RCF may be caused due to asperities interactions because after shot peening the surface roughness of the roller was increased. Film thickness measurements confirmed that the contact is realized actually only between asperity peaks of shot peened ball and smooth disc.Conversely, no negative effect on RCF was observed when the shot peened surface of the roller was polished. The polish of asperity peaks causes the creation of lands and micro-cavities, which may be employed as lubricant micro-reservoirs. From film thickness measurements it has been observed that lubricant emitted by shallow micro-cavities can provide the local increase in lubrication film thickness, which thereby reduces asperities interactions. Similar results were obtained for start-up conditions where the squeeze lubricant enlarges film thickness and reduces surface interactions.From the obtained results, it can be suggested that properly designed surface topography modification could help to increase the efficiency of lubrication films leading to the enhancement of contact fatigue life of non-conformal mixed lubricated rolling/sliding contacts.     

Study of tribological properties of coating/substrate system in micrometer and nanometer scales with a scanning probe microscope

We have used a scanning probe microscope equipped with a custom made diamond tip to study tribological properties of an inorganic–organic hybrid Si, O, H, and C coating produced by plasma enhanced chemical vapor deposition (PECVD) on siloxane/acrylic/polycarbonate multilayer substrates and on glass substrates. The micro indentation hardness and micro mar resistance were measured under different normal forces, and the critical loads for cracking, delamination, and chipping were evaluated. The effects of substrate, coating thickness, and interfacial adhesion on tribological properties of the coating/substrate systems are discussed. The results show that increasing coating thickness and strengthening interfacial adhesion can effectively inhibit cracking, delamination, and chipping of the coating/substrate systems under wear. Improving the physical properties of the PECVD coating and substrate, such as enhancing elastic recovery, reducing plasticity and brittleness, and matching the properties of coating and substrate better can improve the wear resistance of the systems further.     

Fluorinated FeF3 catalyst interactions in three different oil formulations using design of experiment optimization and chemistry characterization of tribofilms

The influence of fluorinated FeF₃ catalyst on the formation and properties of tribofilms was examined using design of experiment (DOE) under extreme boundary lubrication (385 N or maximum Hertzian contact pressure of 2.72 GPa). A closed loop boundary condition test was developed to examine the behaviour of lubricants under boundary conditions. The reduction of phosphorus in engine oil was examined using two different plain oils and one fully formulated oil. Results indicate the formation of a thicker tribofilm in plain fluorinated oil when compared with fluorinated fully formulated oils. Several chemistry combinations were prepared and tested. Wear and frictional properties were evaluated using DOE, and the interactions of fluorinated FeF₃ catalyst with minimum phosphorus were studied and compared with respect to fully formulated and plain zinc dialkyl dithiophosphate oils. Tribofilms with thickness ranging from 150 to 350 nm were developed during wear tests and were analysed for fluorinated plain and fully formulated oils that target reducing phosphorus. Three specific tests with optimised 0.6% FeF₃ catalyst concentrations were used with 0.05% phosphorus in plain and fully formulated oil to verify the model optimised conditions with respect to wear and time to full break down. Scanning electron microscopy, hardness of the tribofilms and Auger spectroscopy confirm the presence of fluorine and phosphorus. These tests confirm the optimised prediction of the DOE model. Copyright © 2011 John Wiley & Sons, Ltd.     

Numerical modeling of processes of mass transfer in tribological contacts by the method of movable cellular automata

Wear is viewed as a stochastic process in the surface layers of contacting bodies; it comprises the processes of spalling of wear particles and their stochastic transportation and nanobonding. These processes can be described within the framework of the macroscopic phenomenological theory [1]; however, the parameters of the macroscopic theory can be found only by microscopic modeling of the tribological interface. In the present paper, the dynamic processes are modeled by means of the method of movable cellular automata in the interface of a tribological couple. The results allow us to identify the parameters of the macroscopic model based on the modeling of processes at the nanolevel; this enables us to extrapolate from the nano- to the macrolevel.     

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.     

Wear transitions and mechanisms in lubricated sliding of a molybdenum coating

Wear tests were performed for a Mo coating sliding against bearing steel specimen under boundary lubrication conditions. Results were compared with (i) hardened carbon steel sliding against bearing steel and (ii) Mo coating sliding against boron cast iron. Tests indicated that the wear resistance of the Mo coating was superior to that of the uncoated hardened steel. The initial surface topographies of the coatings were suitable to facilitate the transfer of the applied load directly onto the phases and prevented the softer phase directly involved in the wear process. The morphology of the transfer layer formed on the Mo coating was identified by X-ray diffractometry. And the layers were expected to supply an in situ lubrication effect. The wear rates of the coating against a steel slider were lower compared with those worn against a cast iron slider. With increasing applied load, the probability of the harder phases crack and fracture increased until the fraction of the unfragmented phases on the contact surfaces was no longer adequate to support the load. The dominant wear mechanisms in each wear regime were discussed.     

A tribological study of an S,P-containing benzotriazole derivative as an additive in pentaerythritol ester

The load-carrying capacity, antiwear and friction reduction properties of an S,P-containing benzotriazole derivative (BMDDP) added to a synthetic lubricant (pentaerythritol ester) were evaluated using a four-ball test machine. The results when compared with those of tricresyl phosphate (TCP) and zinc dialkyldithiophosphate (ZDDP) show that, in pentaerythritol ester, the novel compound (BMDDP) is an excellent multifunctional additive, which possesses better load-carrying capacity, antiwear and friction reduction properties than either TCP or ZDDP. The rubbed surfaces were analysed using XPS and EPMA, and the antiwear mechanism is discussed.     

Study on rotational fretting wear of bonded MoS2 solid lubricant coating prepared on medium carbon steel

The rotational fretting wear behaviors of the bonded MoS₂ solid lubricant coating and its substrate steel were comparatively studied under varied angular displacement amplitudes, constant normal load, and rotational speed. Dynamic analysis in combination with microscopic examinations was performed through SEM, EDX, XPS, optical microscope, and surface profilometer. The experimental results showed MoS₂ changed the fretting running regimes of substrate. The friction coefficients of MoS₂ were lower than those of the substrate. For MoS₂, the damage in partial slip regime was very slight. The damage mechanism of the coating in slip regime was main abrasive wear, delamination, and tribo-oxidation.     

Evaluation of Local Mechanical Properties in Depth in MoDTC/ZDDP and ZDDP Tribochemical Reacted Films Using Nanoindentation

Local mechanical properties in depth and near the surface of MoDTC/ZDDP and ZDDP tribofilms, which exhibited obviously different friction coefficients in a pin-on-disc test, were determined by using a nanoindentation technique combined with in-situ atomic force microscopy (AFM) observation. Tapping-mode AFM observation revealed that the MoDTC/ZDDP film was much rougher than the ZDDP film. Nanoindentation measurement revealed that the MoDTC/ZDDP and ZDDP tribofilms possessed different elasto-plasticities around a depth of several nanometers from the surface, although both films showed the same hardness and modulus depth distributions except in the surface area. The same mechanical depth distributions indicated that both kinds of tribofilm were functionally graded materials; that is, they consisted of a layer near the surface with lower hardness and modulus and providing lubrication and a base layer with higher hardness and modulus and serving to modify property differences at the interface. Most importantly, the different elasto-plasticities near the tribofilm surfaces revealed that the MoDTC/ZDDP tribofilm possessed lower shearing yield stress than the ZDDP tribofilm. The results of this study suggest that the presence of some solid lubricants such as MoS₂ just below the MoDTC/ZDDP film surface reduced the boundary friction coefficient.     

Wear behavior of low-cost, lightweight TiC/Ti–6Al–4V composite under fretting: Effectiveness of solid-film lubricant counterparts

The wear behavior of low-cost, lightweight 10 wt% titanium carbide (TiC)-particulate-reinforced Ti–6Al–4V matrix composite (TiC/Ti–6Al–4V) was examined under fretting at 296, 423, and 523 K in air. Bare 10 wt% TiC/Ti–6Al–4V hemispherical pins were used in contact with dispersed multiwalled carbon nanotubes (MWNTs), magnetron-sputtered diamond-like carbon/chromium (DLC/Cr), magnetron-sputtered graphite-like carbon/chromium (GLC/Cr), and magnetron-sputtered molybdenum disulfide/titanium (MoS₂/Ti) deposited on Ti–6Al–4V, Ti–48Al–2Cr–2Nb, and nickel-based superalloy 718. When TiC/Ti–6Al–4V was brought into contact with bare Ti–6Al–4V, bare Ti–48Al–2Cr–2Nb, and bare nickel-based superalloy 718, strong adhesion, severe galling, and severe wear occurred. However, when TiC/Ti–6Al–4V was brought into contact with MWNT, DLC/Cr, GLC/Cr, and MoS₂/Ti coatings, no galling occurred in the contact, and relatively minor wear was observed regardless of the coating. All the MWNT, DLC/Cr, GLC/Cr, and MoS₂/Ti coatings on Ti–6Al–4V were effective from 296 to 523 K, but the effectiveness of the MWNT, DLC/Cr, GLC/Cr, and MoS₂/Ti coatings decreased as temperature increased.     

Influence of load on the tribological conditions in piston ring and cylinder liner contacts in a medium-speed diesel engine

The present work is an attempt to determine the oil film thickness in a medium-speed four-stroke diesel engine with a cylinder diameter of 200 mm. Experimental research on this topic was found necessary due to the limited amount of published information available with reference to engines of the present size. The experimental part of the study was carried out as firing engine tests, with an instrumented piston, equipped with telemetric data transmission, and an instrumented cylinder liner in a 6-in-line test engine. The study was carried out for different parts of the four-stroke working cycle and for different levels of engine power output. The results were compared with the results of computer simulations, carried out using a commercial software package. The conclusions of the study comprise aspects on the formation and development of the oil film between the rings and the liner under a set of load levels together with the periodical fluctuation during different strokes of the working cycle.