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.     

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.     

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.     

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.     

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.     

Comparing tribological behaviors of sulfur- and phosphorus-free organomolybdenum additive with ZDDP and MoDTC

A new kind of sulfur- and phosphorus-free organomolybdenum oil-based additive N, N-bis (2-hydroxyethyl)-dodecanamide molybdate (NNDM) was prepared. Its tribological performances as additive in base oil 150SN were examined on a four-ball tester, and compared with those of ZDDP and MoDTC under boundary lubrication condition. The tribofilm NNDM generated on the worn surface was analyzed by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Results showed that NNDM blend oil exhibited excellent load-carrying capacity, significantly reduced friction coefficient and wear rate of worn surface, which could be attributed to high amount of long-chain alkylamide and MoO_x in NNDM tribofilm.     

Friction property study of the surface of ZDDP and MoDTC antiwear additive films using AFM/LFM and force curve methods

The friction properties and material differences of the surface of ZDDP and MoDTC antiwear additive films, which give clear evidence of different friction coefficients in a pin-on-disc test, have been studied using atomic force microscopy (AFM)/lateral force microscopy (LFM) and force curve methods. The AFM/LFM observations show that the friction force on the surface of MoDTC additive films over the sliding area of a steel disc is lower and the friction force of ZDDP additive films is higher than that of afilmless area. Lateral force scope-trace evaluations reveal that the ratio of the friction forces on the surface of the ZDDP film, the filmless area, and the MoDTC film under the same normal force is approximately 1.5:1.0:0.7. Force curve measurements indicate that the surface materials of the ZDDP film, thefilmless area, and the MoDTC film differ according to their attractive forces, that is 29 nN for the ZDDP film, 22 nN for the filmless area, and 12 nN for the MoDTC film. These results correspond to the friction behaviour in the pin-on-disc test and also agree with the idea of the formation of solid MoS₂ lubricant from MoDTC additives on the surface of the antiwear film.     

Improved mixed and boundary lubrication with glycerol-diamond technology

Abstract

The 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 extensively studied as ultralow friction films to protect the surfaces of ductile metals for space applications are expected to fulfil this part. The main purpose of this work is to investigate the friction and wear properties of glycerol lubricated DLC coatings under boundary lubrication conditions. The DLC material consists of tetrahedral hydrogen free amorphous diamond-like carbon (denoted as ta-C) as shown by the time of flight secondary ion mass spectroscopy (ToF-SIMS) analyses and the nanoindentation measurements. The friction coefficient below 0&middot.01, called superlubricity, and no measurable wear were obtained by sliding the ta-C/ta-C friction pair in the presence of pure glycerol as a lubricant at 353 K. The mechanism by which glycerol is able to reduce the friction in the millirange was revealed by ToF SIMS analyses inside and outside wear scars formed by friction experiments using deuterated glycerol and ¹³C glycerol.     

Antagonistic Interaction of Antiwear Additives and Carbon Black

It is well known that the presence of soot in engine oils can lead to an increase in wear of engine parts. This is a growing problem as soot levels in diesel engine oils are rising due to a combination of extended drain intervals and the various methods employed to reduce NO _x formation such as retarded ignition and exhaust gas recirculation. Several different mechanisms have been proposed by which soot might lead to an increase in wear in mixed lubrication conditions, of which the most widely favoured is abrasion by soot, either of the rubbing metallic parts in engines or of the antiwear additive films formed on rubbing metal surfaces. In this study it is shown that the combination of mixed alkyl ZDDP and carbon black (used as soot surrogate) is strongly antagonistic in terms of wear. In a lubricant containing carbon black, the presence of ZDDP leads to considerably more wear than if ZDDP is left out. A similar, though less severe antagonism is also seen with primary ZDDP and other antiwear and EP additives. By varying the lubricant film thickness it is shown that the effect of carbon black in ZDDP-containing oils is to promote wear up to quite thick hydrodynamic film conditions, approaching the secondary carbon black particle size. It is proposed that the antagonistic wear effect results from a corrosion-abrasive mechanism in which the reaction film formed by antiwear additive and rubbing metal surface is very rapidly and continually abraded by carbon black. At most carbon black concentrations, wear rate then becomes controlled by the rate of initial antiwear additive film formation, which for secondary ZDDP is very rapid, rather than by the kinetics of the abrasive process. From this understanding, strategies for reducing the impact of engine soot on wear can be deduced.     

Tribological Behaviors of Different Diamond-Like Carbon Coatings on Nitrided Mild Steel Lubricated With Benzotriazole-Containing Borate Esters

Three synthesized benzotriazole-containing borate esters were separately added into poly-alpha-olefin (PAO) as additives, using molybdenum dithiocarbamate (MoDTC) as the comparison. The friction and wear behavior of Ti-DLC and Ti/Al-DLC coating on nitrided AISI-1045 steel sliding against AISI 52100 steel under the lubrication of PAO containing various additives was evaluated using a reciprocating ball-on-disk friction and wear tester. The morphology and chemical feature of the worn surfaces of the DLC coatings were observed and analyzed using a three dimensional (3D) surface profiler, a scanning electron microscope (SEM), and an X-ray photoelectron spectroscope (XPS). Results show that the three kinds of benzotriazole-containing borate esters as additives in PAO had much better tribological properties than MoDTC; the wear resistance of Ti/Al-DLC coating was better than Ti-DLC coating.     

Additive–additive interaction: an XPS study of the effect of ZDDP on the AW/EP characteristics of molybdenum based additives

The effect of zinc dialkyldithiophosphate (ZDDP) addition on the antiwear (AW) and extreme pressure (EP) properties of molybdenum dialkyldithiocarbamate (MoDTC) and molybdenum dialkyl dithiophosphate (MoDTP) are evaluated by standard Four-Ball friction test and also by the determination of coefficient of friction using an oscillating SRV apparatus. The boundary lubrication film formed on the worn surface using the two molybdenum additives and their combination with ZDDP is investigated by depth profile X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) to find out the chemistry of tribochemical reaction occurring at the surface during friction. It is seen that MoDTP possesses better AW properties than MoDTC due to its high reactivity with the metal surface. Nevertheless, the AW characteristics of MoDTC could be improved by the addition of ZDDP. The frictional properties of MoDTP, however, do not change by the addition of ZDDP. The synergistic action of ZDDP on MoDTC is attributed to the enhanced decomposition of MoDTC in presence of ZDDP. This is tentatively explained in terms of some interaction of zinc with the electron donating nitrogen present in MoDTC, which would have helped to increase its tribo-reactivity. XPS studies revealed that in the presence of ZDDP, MoDTC form mainly metal sulphides like MoS₂ and FeS under friction. The MoDTP+ZDDP derived surface, on the other hand, produced mainly metal phosphate along with molybdenum oxysulphides and small amount of MoS₂ and FeS. The mechanism of action of additives is explained.     

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.     

Tribological Dependence of the High-Performance Ferrous-Based Coating on Different Coating Counterparts in Engine Oil

A ferrous-based coating with significant chromium was fabricated on aluminum alloy substrate using a plasma spray technique. The tribological performance of the as-fabricated ferrous-based coating sliding against different coatings including Cr, CrN, TiN, and diamond-like carbon (DLC) in an engine oil environment were comparatively studied. Results showed that the high hardness of the sprayed ferrous-based coating was achieved due to the dispersion strengthening effect of Cr₇C₃ phase embedded in the austenite matrix. The ferrous-based coating exhibited low friction coefficients when coupled with these four coating counterparts, which could be attributed to the boundary lubricating effect of engine oil. However, both friction and wear of the ferrous-based coating were different when sliding against these different coating counterparts, which might be closely related to the surface roughness, self-lubricating effect, and mechanical properties of the coupled coatings. Ferrous-based coating sliding against CrN and DLC coatings exhibited good tribological performance in engine oil. The best coating counterpart for the ferrous-based coating in an engine was DLC coating.     

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.     

Surface and Tribological Characteristics of Tribofilms Formed in the Boundary Lubrication Regime with Application to Internal Combustion Engines

One of the biggest challenges in engine tribology is to formulate appropriate lubricants, which will increase fuel efficiency by reducing friction, yet still provide good wear resistance. The lubricant should also be formulated to limit particulate and gaseous exhaust emissions to the levels allowed by current regulations. In real lubricant formulations there can be 10–15 additives and the interactions between additives must be taken into account. The effects of eliminating the friction modifier and friction modifier plus anti-wear additive zinc dialkyl dithiophosphate (ZDDP) from the additive package of fully formulated lubricants on friction, wear and wear film forming characteristics have been examined. Tests have been conducted under lubricated wear conditions at bulk oil temperatures of 20, 50, and 100 °C using a reciprocating pin-on-plate tribometer. Boundary lubrication conditions were varied according to the value of starting lambda ratio. The wear film has been examined by Energy Dispersive X-ray analysis (EDX) and X-ray Photoelectron Spectroscopy (XPS). In order to investigate the morphology of the reaction films formed by the additive packages of these lubricants, Atomic Force Microscopy (AFM) was used. In this paper it has been shown that tribofilms, derived from ZDDP/surface interactions, affect friction, the extent of which is determined by tribological conditions. Detergent interactions with ZDDP enhance the complexity of the tribofilm and enrich the level of C in the film whilst affecting the friction and wear response. Through integration of tribological measurements and surface analysis, progress towards improving the nature of interactions is made and forms the focus of the paper.     

ZDDP and MoDTC interactions and their effect on tribological performance – tribofilm characteristics and its evolution

In this work, the interactions between two key additives in current lubricants (ZDDP and MoDTC) and the effect on tribofilm formation and tribofilm evolution under boundary lubrication are studied. The chemical and tribological characteristics of the tribofilms are probed using measurement of friction, wear and film characteristics. Tribofilms have been examined by energy dispersive X-ray analysis (EDX) and X-ray photoelectron spectroscopy (XPS). In order to investigate the morphology of the reaction films formed, atomic force microscopy (AFM) was used. In this work, for the first time, a link between a proposed MoDTC breakdown mechanism and MoDTC tribofilm characteristics, measured on experimentally derived tribofilms, is made.     

The effect of ZDDP and MoDTC additives in engine oil on the friction properties of DLC‐coated and steel cam followers

Friction tests simulating cam follower sliding conditions were conducted using a pin‐on‐disc test rig. In the case of SAE 5W‐30 class engine oil, the friction coefficient of the combination of steel pins sliding on a steel disc increased from 0.11 to 0.12, while that of steel pins sliding on a diamond‐like carbon (DLC)‐coated disc decreased from 0.12 to 0.10. For 5W‐20 oil containing the friction modifier MoDTC (molybdenum dithio‐carbamates), the friction coefficient of steel pins sliding on a steel disc decreased markedly from 0.12 to 0.04. In contrast, that of steel pins sliding on a DLC‐coated disc decreased more moderately, from 0.11 to 0.08. In both cases, Zn, P, S, and Mo elements derived from ZDDP (zinc dialkyldithiophosphate) and MoDTC additives were not detected on the DLC‐coated disc, while these elements were detected on the steel disc and pins using electron probe microanalysis and X‐ray photo‐electron spectroscopy surface analysis. It appears that a tribochemical reaction film did not form on the DLC material due to its inactive chemical properties. Therefore, an increase in friction due to the formation of the film derived from ZDDP and a decrease in friction due to the formation of the film derived from MoDTC were clearly suppressed in the case of the steel pins sliding on the DLC‐coated disc. It is thought that the tribo‐chemical reaction film was instrumental in reducing friction substantially. The lateral force of the film formed on the steel disc was then measured using an atomic force microscopy lateral force microscopy test. The lateral force of the film resulting from the 5W‐30 oil was much higher than that of the film formed from the 5W‐20 oil with MoDTC. This result coincided well with the results of the friction tests. Judging from these results, it is thought that the high friction coefficient observed for the steel pins on the steel disc for the 5W‐30 oil was caused by the higher shear strength of the film formed from ZDDP. On the other hand, the very low friction coefficient observed for the steel pin‐steel disc combination for the 5W‐20 oil was presumably caused by the formation of a solid MoS₂ lubricant from the MoDTC additive.     

The Wear Resistance of HVOF Sprayed Composite Coatings

The aim of the study was to determine the interactions between standard antiwear zinc dialkyldithiophosphate (ZDTP)-type additives and composite coatings containing hard phases of Al₂O₃, SiC, and TiN in the nickel matrix. The analysis was conducted for selected ceramic materials with different structures and different tribological behavior of ionic, covalent, and metallic bonds. The composite coatings were deposited on C45 steel using the high-velocity oxygen-fuel (HVOF) process. This process efficiently uses high kinetic energy and controlled thermal output to produce dense, low porosity coatings with highly predictable chemistries that are homogeneous in structure. The coatings can operate under harsh service conditions, because they are characterized by higher durability and higher wear and corrosion resistance. It was necessary to determine the interactions between the ZDTP-type antiwear additives (zinc dialkyldithiophosphates) and the coatings. The tribological properties of nickel and nickel-based composite coatings were examined by means of a T-01 M tester functioning in the ball-on-disc configuration during technically dry friction and boundary lubricated friction with lubricants containing 1% ZDTP. The comparative analysis confirmed different tribochemical activity and, accordingly, different tribological effectiveness of the nickel and nickel-based composite coatings during friction.     

In Situ Raman Observations of the Formation of MoDTC-Derived Tribofilms at Steel/Steel Contact Under Boundary Lubrication

ABSTRACT

In this study, the time-dependent formation process of molybdenum dithiocarbamate (MoDTC)-derived tribofilms at steel/steel contact under boundary lubrication was investigated by using an in situ Raman tribometer. Especially, we focused on the effects of zinc dialkyldithiophosphate (ZDDP) concentration in MoDTC solution on MoDTC tribofilm formation process. A laboratory-built in situ Raman tribometer was used to evaluate friction and the formation process of MoDTC-derived tribofilms. All our results clearly suggest that there is an optimum ZDDP concentration in MoDTC solution for promoting the formation of MoS₂ tribofilms on the sliding surfaces, and there is also a threshold value for the formation rate of MoS₂ on the sliding surface for achieving low friction under lubrication with MoDTC-containing lubricants.     

The Tribological Performance of S-[2-(Acetamido) Benzothiazol-1-yl] N,N-Dioctyl Dithiocarbamate as an Additive in Rapeseed Oil

A new derivative of benzothiazol, S-[2-(acetamido) benzothiazol-1-yl] N,N-dioctyl dithiocarbamate, was synthesized. The tribological behavior of the synthesized compound as an additive in rapeseed oil was evaluated using a four-ball friction and wear tester, and compared with that of zinc butyloctyl dithiophosphate (ZDDP) and zinc dibutyl dithiocarbamate (ZDTC). The morphologies and elemental chemical states on the worn surfaces of the lubricated GCr15 steel were investigated by means of X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The biodegradability (fate) and microbial toxicity (effects) measurement of the additive were also performed. The results indicate that the compound possesses excellent load-carrying capacity, antiwear and friction-reducing properties as compared with rapeseed oil alone. The antiwear and friction reduction properties of the novel compound are similar to those of ZDDP and ZDTC; and its load-carrying capacity is similar to ZDTC, but is better than ZDDP. The excellent tribological behavior of the novel compound is attributed to chemical adsorption on and tribochemical reaction with the steel surface, with the generation of a surface protective film composed of FeS, FeSO₄, etc. Measurements of biodegradability and microbial toxicity show that the additive has high biodegradability, and microbial toxicity needed to be further lowered.