Behaviour of lubricant additives on DLC coatings

Non-ferrous surfaces such as diamond-like carbon (DLC) coatings are becoming potential candidates for automotive engine parts because of fuel economy gains that these surfaces offer by operating with very low friction. In recent years, a wide range of DLC coatings have been developed and it is important to understand their film-forming, friction reduction and wear resistance mechanisms under lubricated conditions. This aim of the work described in this thesis is to improve our understanding of the tribological behaviour of DLC coatings with different engine oil additives. The main focus of the thesis is to study a wide range of available DLC coating types with currently available and widely-used additives such as ZDDP, friction modifiers, MoDTC etc., in order to establish general rules of their tribological behaviour that will help lubricant manufacturers produce new oil formulations. The research shows that tribofilms are formed on all DLCs by most of the currently used additives and that the film thickness depends on various factors such as type of DLC coating, doping elements present in the coatings, concentration of hydrogen and tungsten present in the coatings and the counterpart. Hydrogen-free coatings (a-C and ta-C) give lower boundary friction compared to the other coatings whereas hydrogenated amorphous carbon (a-C:H) coatings give better wear resistance properties. Study of a-C:H:W coatings shows that the concentration of tungsten present in the coatings has a significant influence on wear resistance properties but negligible influence on the friction properties when additives are present. The steel/steel couple is known to form a thick ZDDP tribofilm. If one of the contact surfaces is coated with DLC, the tribofilm forming properties on the steel vary and, for some cases, the low boundary friction properties of DLCs are degraded

Friction and wear behaviour of Mo − W doped carbon-based coating during boundary lubricated sliding

A molybdenum and tungsten doped carbon-based coating (Mo−W−C) was developed in order to provide low friction in boundary lubricated sliding condition at ambient and at high temperature. The Mo−W−C coating showed the lowest friction coefficient among a number of commercially available state-of-the-art DLC coatings at ambient temperature. At elevated temperature (200°C), Mo−W−C coating showed a significant reduction in friction coefficient with sliding distance in contrast to DLC coatings. Raman spectroscopy revealed the importance of combined Mo and W doping for achieving low friction at both ambient and high temperature. The significant decrease in friction and wear rate was attributed to the presence of graphitic carbon debris (from coating) and 'in-situ' formed metal sulphides (WS2 and MoS2, where metals were supplied from coating and sulphur from engine oil) in the transfer layer

Tribological performance and tribochemical processes in a DLC/steel system when lubricated in a fully formulated oil and base oil

Diamond-like carbon (DLC) coatings show extremely good promise for a number of applications in automotive components as they exhibit excellent tribological properties such as low friction and good wear resistance. This can impact on improved fuel economy and durability of the engine components. Much work has been reported on the dry sliding of DLC coatings with less so in lubricated contacts and, as such, there is a need to further understand the tribochemistry of lubricated DLC contacts. Commercially-available oils are normally optimised to work on ferrous surfaces. Previous studies on DLC lubricated contacts have tended to use model oil systems rather than fully formulated lubricants and from this an interesting picture of lubrication mechanisms is emerging. Optimising compatibility between a surface and a set of lubricant additives may lead to excellent durability (wear) as well as increased fuel economy (low friction). In this work, the friction and wear properties of a DLC coating under boundary lubrication conditions have been investigated and the tribological performance compared with that of an uncoated steel system. A pin-on-plate tribotester was used to run the experiments using High speed steel (HSS) M2 grade plates coated with 15 at.% hydrogenated DLC (a-C:15H) sliding against cast iron pins. A Group III mineral base oil, fully synthetic Group IV PAO and four different fully formulated oils were used in this study. Furthermore optical and scanning electron microscopes (SEM) were used to observe the wear scar and to assess the durability of the coatings. Energy-Dispersive X-ray analysis (EDX), X-ray Photoelectron Spectroscopy (XPS) and Raman spectroscopy analyses were performed on the tribofilms to understand the tribochemical interactions between oil additives and the a-C:15H coating. This study show that the durability of the a-C:15H coating strongly depends on the selected additive package in the oils. In addition the effect of detergent, dispersant and antioxidants on the performance of the molybdenum-based friction modifier (Mo-FM) and ZDDP anti-wear additive was investigated and results are reported in this paper

The influence of anti-wear additive ZDDP on doped and undoped diamond-like carbon coatings

Diamond-like carbon (DLC) coatings are recognised as a promising way to reduce friction and improve wear performance of automotive engine components. DLC coatings provide new possibilities in the improvement of the tribological performance of automotive components beyond what can be achieved with lubricant design alone. Lubricants are currently designed for metallic surfaces, the tribology of which is well defined and documented. DLC does not share this depth of tribological knowledge; thus, its practical implementation is stymied. In this work, three DLC coatings are tested: an amorphous hydrogenated DLC, a silicone-doped amorphous hydrogenated DLC and a tungsten-doped amorphous hydrogenated DLC. The three coatings are tested tribologically on a pin-on-reciprocating plate tribometer against a cast iron pin in a group III base oil, and a fully formulated oil that consists of a group III base oil and contains ZDDP, at 100°C for 6 h and for 20 h in order to determine whether a phosphor-based tribofilm is formed at the contact. The formation of a tribofilm is characterised using atomic force microscopy and X-ray photoelectron spectroscopy techniques. The main findings of this study are the formation of a transfer film at the undoped, amorphous hydrogenated DLC surface, and also the tungsten amorphous hydrogenated DLC having a significant wear removal during the testing. The three coatings were found to have differing levels of wear, with the tungsten-doped DLC showing the highest, the silicon-doped DLC showing some coating removal and the amorphous hydrogenated DLC showing only minimal signs of wear

Tribological performance of an H-DLC coating prepared by PECVD

Carbon-based coatings are of wide interest due to their application in machine elements subjected to continuous contact where fluid lubricant films are not permitted. This paper describes the tribological performance under dry conditions of duplex layered H-DLC coating sequentially deposited by microwave excited plasma enhanced chemical vapour deposition on AISI 52100 steel. The architecture of the coating comprised Cr, WC, and DLC (a-C:H) with a total thickness of 2.8 μm and compressive residual stress very close to 1 GPa. Surface hardness was approximately 22 GPa and its reduced elastic modulus around 180 GPa. Scratch tests indicated a well adhered coating achieving a critical load of 80 N. The effect of normal load on the friction and wear behaviours were investigated with steel pins sliding against the actual coating under dry conditions at room temperature (20 ± 2°C) and 35-50% RH. The results show that coefficient of friction of the coating decreased from 0.21 to 0.13 values with the increase in the applied loads (10-50 N). Specific wear rates of the surface coating also decrease with the increase in the same range of applied loads. Maximum and minimum values were 14 × 10-8 and 5.5 × 10-8 mm-3/N m, respectively. Through Raman spectroscopy and electron microscopy it was confirmed the carbon-carbon contact, due to the tribolayer formation on the wear scars of the coating and pin. In order to further corroborate the experimental observations regarding the graphitisation behaviour, the existing mathematical relationships to determine the graphitisation temperature of the coating/steel contact as well as the flash temperature were used

A Semi-deterministic Wear Model Considering the Effect of Zinc Dialkyl Dithiophosphate Tribofilm

Tribochemistry plays a very important role in the behaviour of systems in tribologically loaded contacts under boundary lubrication conditions. Previous works have mainly reported contact mechanics simulations for capturing the boundary lubrication regime, but the real mechanism in which tribofilms reduce wear is still unclear. In this paper, the wear prediction capabilities of a recently published mechanochemical simulation approach (Ghanbarzadeh et al. in Tribol Int, 2014) are tested. The wear model, which involves a time- and spatially dependent coefficient of wear, was tested for two additive concentrations and three temperatures at different times, and the predictions are validated against experimental results. The experiments were conducted using a mini-traction machine in a sliding/rolling condition, and the spacer layer interferometry method was used to measure the tribofilm thickness. Wear measurements have been taken using a white-light interferometry. Good agreement is seen between simulation and experiment in terms of tribofilm thickness and wear depth predictions

In situ synchrotron XAS study of the decomposition kinetics of ZDDP triboreactive interfaces

One of the major obstacles in replacing the widely used zinc dialkyldithiophosphate (ZDDP) antiwear additive with a more environmentally friendly one is the difficulty of time-resolving the surface species resulting from its decomposition mechanism under high contact pressure and temperature. To tackle this issue, a newly developed miniature pin-on-disc tribotester was coupled with synchrotron X-ray absorption spectroscopy (XAS) to perform in situ tribological tests while examining the composition of the formed triboreactive films. The results showed that in the case of bare steel surfaces the initial decomposition products are mainly zinc sulfate species, which with further shearing and heating are reduced to zinc sulfide mixed with metal oxides. The mixed base layer seems to enhance the tenacity of the subsequently formed zinc phosphate layers composing the main bulk of the protective triboreactive film. This base layer was not observed in the case of coated substrates with hydrogenated diamond-like carbon (a-C:H DLC) coating, which results in the formation of less durable films of small volume barely covering the contacting surfaces and readily removed by shear. Comprehensive decomposition pathways and kinetics for the ZDDP triboreactive films are proposed, which enable the control and modification of the ZDDP triboreactive films