ZDDP Tribofilm Research Articles

ZDDP Tribofilm Formation and Removal

While ZDDP tribofilm formation has been widely studied, the mechanism of ZDDP tribofilm removal during rubbing is still unclear. The study employs a ball on disc tribometer to monitor ZDDP tribofilm development in rolling-sliding, mixed lubrication conditions. It is found that when ZDDP tribofilms are formed very rapidly, as is the case with short alkyl chain, secondary ZDDPs, a large proportion of the initially-formed tribofilm is suddenly lost during rubbing. By contrast, the tribofilms that form more slowly from primary ZDDPs and longer chain secondaries are not partially lost during rubbing. XPS analysis showed that a rapidly-formed tribofilm before its partial removal has a very small Zn/O ratio, and a high BO/NBO. This suggests that such tribofilm contains a significant proportion of ultraphosphate, which is likely to have a relatively weak structure due to lack of stabilising cations. This may result in the tribofilm being partially removed when it reaches a certain thickness. By comparison, the remaining tribofilm, and also tribofilms that form slowly, have high Zn/O and low BO/NBO. This suggests that they consist of short chain polyphosphates and are thus stronger and more durable.Graphical

Tribological manufacturing of ZDDP tribofilms functionalised by graphene nanoplatelets

Abstract 3D Tribo-Nanoprinting (3D TNP), which uses a highly controllable tribological contact to deposit tribofilms, has been proposed as a manufacturing method for nanoscale structures. Inspired by this, we show for the first time, as a proof of concept, the ability to electrically functionalise tribofilms for potential use in the manufacture of structures with nanoscale thickness. Zinc dialkyldithiophosphate (ZDDP) tribofilms have been generated to include varying concentrations of graphene nanoplatelets (GNPs) resulting in them becoming electrically conductive when tested using conductive atomic force microscopy. In its highest GNP concentration, approximately 55% of the surface of the tribofilm was able to sustain current up to a threshold of 245 pA. The higher graphene content led to a suppression in film formation and decreased substrate coverage. Transmission electron microscopy revealed a dual-layered tribofilm with a carbon-rich layer above a pure layer of ZDDP tribofilm. Within the carbon-rich layer, the GNPs formed into scrolls which created an internal network through which current could flow, being limited by the insulating pure ZDDP layer at the film-substrate interface, and the presence of surface graphene sheets. A modified lateral force microscopy procedure supported the presence of surface graphene sheets. Despite limited deposition precision in terms of homogeneity and distribution of the tribofilms, this work provides a step towards the use of 3D TNP for the manufacture of electronic structures on the nanoscale by proving that tribofilms can be functionalised by the addition of particle additives.

Mechanical properties of tribofilms formed by metal dithiodiphosphates

Lubrication-based tribofilms are crucial in protecting contacting parts from wear and friction. A popular and well-studied additive commonly used in tribofilm formation is zinc dialkyldithiophosphate (ZDDP). While ZDDP has been shown to be an effective additive, the use of other metals in place of zinc may provide further benefits. Tribofilms were generated using fluids which contained DDPs neutralized with octylamine or different metals: magnesium, titanium, and zinc. Tribofilms were formed at 30 min, 60 min, and 120 min and were chemically and mechanically analyzed using EDS, AFM, and nanoindentation. Tribofilms were also analyzed based on property differences at the peak surface interactions. The metal used was found to have a significant effect on both tribofilms morphology and mechanical properties. Properties were further seen to change in the top 10% of the tribofilm surface as compared to bulk surface properties. Hardness and elastic modulus ratios were higher for the tribofilms formed by octylamine and MDDP as compared to TDDP and ZDDP tribofilms, but with the tradeoff of less tribofilm coverage of the substrate.

Preparation and tribological study of novel amide-based organic friction modifiers

We have synthesized two novel amide-based organic friction modifiers(OFMs), namely NIPAOA and NDEAOA, through the addition reaction of oleamine with N-isopropylacrylamide and N, N-dimethylacrylamide. The two OFMs exhibit good solubility in PAO6 base oil. Their tribological performance has been investigated using a line contact both individually and when compounded with the anti-wear additive zinc dialkyldithiophosphate (ZDDP) at temperatures ranging from 40 ℃ to 130 ℃. The results show that NIPAOA and NDEAOA form dual-site adsorption on the tribo-pair surface through the N and O atoms in the head group amide, resulting in the tribo-film exhibiting excellent friction-reducing performance in PAO6 across the temperatures. When compounded with ZDDP, they both exhibit effective synergistic friction-reducing effects, attributed to the formation of a unique tribo-chemical reaction film on the worn surface that contains almost no Fe and its compounds. The formation of the unique tribo-film is partly due to the continuous adsorption of free OFMs on the surface of the formed ZDDP tribo-film, providing a milder contact environment for the tribo-pair, allowing for the continuous polymerization of medium and long-chain zinc dialkyldithiophosphate (ZDDP) to ultimately form a uniform and flat tribo-chemical reaction film which interspersed with nitrogen-containing compounds. Even after long-term testing, the film maintains good stability and abrasion resistance, effectively synergizing friction-reducing and anti-wear properties.

Tribological responses of steels to different surface films generated in oil lubricants

PurposeThe aim of this study is to experimentally analyze the friction and wear responses of different steels to different surface films generated in oil-lubricated tribological contacts.Design/methodology/approachTribological experiments were conducted using a 100Cr6 bearing ball sliding against a V155 carbon steel disk and 316L stainless steel disk, respectively. Lubricants with additives known to form zinc dialkyl-dithiophosphate (ZDDP) or Ca tribofilms were used.FindingsBoth of the ZDDP and Ca tribofilms helped stabilize the friction coefficient of the carbon steel and stainless steel. The ZDDP tribofilm could effectively protect the carbon steel from wear, in contrast to the stainless steel, whereas the wear of both carbon steel and stainless steel could be significantly reduced by the Ca tribofilm. In the case of neither ZDDP nor Ca tribofilms formation, the 100Cr6 ball was worn by the V155 disk and generated a special surface topography. A polishing wear mechanism was proposed to explain the wear of the 100Cr6 ball.Originality/valueThis study clearly shows the different friction and wear responses of steels to the different surface films and the response is dependent on the tested steel.

What stress components drive mechanochemistry? A study of ZDDP tribofilm formation.

Zinc dialkyldithiophosphate (ZDDP), the most widely used antiwear additive in engine oils, has been extensively studied over the last few decades to help understand the origin of its effectiveness. Glassy phosphate-based tribofilms, approximately 100 nm thick, are often formed on surfaces sliding in ZDDP-containing oils, which help to prevent or reduce wear. Recent studies reveal that a combination of applied shear and compressive stresses drive mechanochemical reactions that promote tribofilm growth, and that growth is further accelerated by increased temperature. While recent work has shown that compressive stress alone is insufficient to form tribofilms, the individual effects of the shear stress and compressive stress are not fully understood. Here, shear and compressive stresses are studied separately by using different ratios of high-viscosity, high-traction fluids for testing. This allows the areal mean compressive and shear stresses in the fluid when confined at a loaded sliding interface, to be independently controlled while driving tribofilm growth, which is a system we refer to as a stress-controlled mechanochemical reactor. Tribofilms derived from a secondary ZDDP were generated using a tungsten carbide/tungsten carbide ball-on-disk contact in the full elastohydrodynamic lubrication (EHL) regime using a mini-traction machine (MTM), meaning that solid-solid contact is avoided. The MTM was equipped with a spacer layer imaging (SLIM) capability, permitting in situ measurement of the tribofilm thickness during its growth. The well-separated sliding surfaces generated by the high-viscosity fluids confirm that solid-solid contact is not required for tribofilm formation. Under these full fluid film EHL conditions, shear stress and temperature promote tribofilm growth in accordance with stress-augmented thermal activation. In contrast, under constant shear stress and temperature, compressive stress has the opposite effect, inhibiting tribofilm growth. Using the extended Eyring model for shear- and hydrostatic pressure-affected reaction kinetics, an activation energy of 0.54 ± 0.04 eV is found, consistent with prior studies of ZDDPs. The activation volume for shear stress is found to be 0.18 ± 0.06 nm3, while that for the compressive stress component is much smaller, at 0.010 ± 0.004 nm3. This not only confirms prior work supporting that shear stress drives tribofilm growth, but demonstrates and quantifies how compressive stress inhibits growth, consistent with the rate-limiting step in tribofilm growth involving a bond-breaking reaction. Implications of these findings are discussed.

Effects of summit radius on the growth of ZDDP tribofilm

Effects of summit radius on the growth of ZDDP tribofilm

ZDDP Tribofilm Formation from a Formulated Oil on Textured Cylinder Liners

Surface texturing can improve lubrication and entrap wear debris but increases the effective roughness of the surfaces, which can induce higher contact pressures. On the one hand, this can be detrimental, but on the other hand, the increase in contact pressure could be used to activate the formation of a ZDDP tribofilm from fully-formulated lubricants. This work investigates the synergistic effect between surface texturing via Maskless Electrochemical Texturing (MECT) and ZDDP additive. The surface texture consisted of an array of annular pockets manufactured on a gray cast iron cylinder liner. These textured surfaces were evaluated by scanning electron microscope (SEM) and energy-dispersive X-ray spectroscopy (EDX). The results indicated that surface texturing via MECT changes the chemical composition of the surfaces, by inducing a preferential dissolution of the metal matrix. Consequently, it exposed the carbon present in the material. The tribological performance was evaluated by a ring-on-cylinder-liner tribometer in reciprocating sliding under boundary lubrication conditions using both a base oil and a commercial formulated oil containing ZDDP additive. For comparison, a commercially honed liner was also tested. After the tribological tests, the surfaces were evaluated by white light interferometry and SEM/EDX. Although the textured surfaces showed higher friction, they induced more ZDDP-tribofilm formation than conventional cylinder liner finish.

Effects of Increasing Contact Stress of Single Asperity on the Growth Process of ZDDP Tribofilm by Surface Roughness

Effects of Increasing Contact Stress of Single Asperity on the Growth Process of ZDDP Tribofilm by Surface Roughness

Effect of Surface Topography on ZDDP Tribofilm Formation During Running-in Stage Subject to Boundary Lubrication

Experimental investigations have been conducted to study the effects of surface topography on ZDDP (zinc dialkyldithiophosphate) chemical tribofilm formation during running-in stage under boundary lubrication conditions. The scope of presented work has been limited and focused on reciprocating motion under boundary lubrication to simulate the upper and lower dead centre of piston ring movement, which is prone to adhesive wear failure. Several surface topographies were designed and fabricated to measure, compare coefficient of friction and ZDDP critical time of tribofilm formation. Rubbing surfaces and their corresponding tribofilms were characterized by SEM and EDX. Mechanisms of surface topography effects on the critical time of ZDDP tribofilm formation is presented and discussed. Results from this study have demonstrated that the surface topography has a significant influence on the critical time of ZDDP tribofilm formation during running-in process and corresponding wear performance. This research provides an opportunity to augment anti-wear performance under boundary lubrication condition. This can be achieved by optimizing surface morphology design to influence the formation of anti-wear tribofilms during the running-in stage. In turn, this will result in interacting component’s service life enhancement and significant cost savings from mitigated wear.

Influence of temperature on wear performance of greases in rolling bearings

Purpose Rolling bearing operation under mixed and boundary lubrication conditions may lead to heavy adhesive or abrasive wear, which may lead to wear-induced rolling bearing failure. The purpose of this paper is to investigate the wear protection capabilities of different grease compositions at varying temperatures. It is considered that the temperature influences the lubrication conditions, the behaviour of grease components, namely, bleed oil and thickener, as well as the tribofilm formation due to tribo-chemical interactions between additives and surfaces. Design/methodology/approach In this study, four different greases were produced on the basis of a mineral base oil by varying the thickener and the addition of ZDDP. Various grease-lubricated rolling bearing experiments were conducted in a wide temperature range from 0°C to 120°C. Subsequently, the wear pattern, tribofilm formation and grease structures were analysed. Thereby, the influence of the different grease thickeners and the performance of ZDDP as a common antiwear and extreme pressure additive was evaluated. Findings The results show a strong temperature-dependency and allow a classification of temperature ranges concerning wear protection. At low temperatures, all greases provide a very good wear protection without the evidence of additive-based tribofilm formation. In the experiments at elevated temperatures, ZDDP tribofilms were formed. The formation depends on the thickener type: in comparison to lithium thickener, polyurea thickener favours more protective tribofilms at the same temperature. The experimental results show that medium temperatures in the range of 40°C–60°C are critical concerning wear due to the insufficient tribolayer formation and limited load carrying capacity of the grease. Originality/value Temperature is a key operating parameter for grease lubrication in roller bearings. The experimental work enables consideration of different impact pathways of temperature by combining roller bearing tests and microanalysis.

Influence of Black Oxide Coating on Micropitting and ZDDP Tribofilm Formation

Micropitting is a type of surface fatigue damage that occurs in rolling–sliding contacts operating under thin oil film conditions. Application of black oxide (BO) coating to steel rubbing surfaces has been suggested as a potential approach to alleviate micropitting. This article confirms that BO coatings can prevent micropitting and identifies the predominant mechanism by which this occurs. Micropitting tests were carried out using zinc dialkyldithiophosphate (ZDDP) solutions in a ball-on-disc tribometer. Micropitting was preferentially generated on the smooth balls and this was completely prevented by applying a BO coating to the rougher discs, regardless of whether the balls were coated or not. In contrast, when the rough discs were not BO-coated, micropitting was consistently generated on both BO-coated and uncoated balls. BO coating has about one-quarter the hardness of the steel used and was found to be very rapidly removed from the surface asperity peaks at the onset of rubbing, despite the presence of ZDDP. This resulted in an almost immediate and very large reduction in the surface roughness of the discs, and this prevented high asperity stresses that would normally initiate and propagate the surface fatigue cracks, leading to micropitting. Parallel measurement showed that BO did not suppress tribofilm growth, so the ZDDP was able to protect against adhesive wear while not promoting micropitting. The insights presented here can help with the design of components and lubricants that are effective in controlling both sliding wear and micropitting.

An Assessment of the Effect of Relative Humidity on the Decomposition of the ZDDP Antiwear Additive

The effect of relative humidity on the decomposition reaction of zinc dialkyldithiophosphate (ZDDP) additive under boundary lubrication regime has been investigated using Raman spectroscopy and atomic force microscopy (AFM). The ZDDP tribofilms were formed using the pin-on-disc tribometer at 30 and 90% relative humidity, which was controlled using a custom-made humid chamber. The results suggest that relative humidity does not change only the length of the phosphate chains but also their affinity towards the available cations. At low relative humidity, zinc pyrophosphate to polyphosphate chains were formed compared to predominantly shorter iron orthophosphate chains at high relative humidity. In addition, relative humidity altered the structure of the mature tribofilm. At low relative humidity, the tribofilm had a patchy structure with average thickness of 140 nm and fractal dimension of 2.17. However, at high relative humidity, the tribofilm had a thin dendritic structure with average thickness of 85 nm and fractal dimension of 2.34. This means that the structure is more complex with a larger number of nesting self-similar structures at all scales. This is significant in making the transition from descriptive towards quantitative information of the tribofilm structure.

Influence of Steel Surface Composition on ZDDP Tribofilm Growth Using Ion Implantation

This paper examines the influence of steel surface composition on antiwear tribofilm formation by ion-implanting typical steel alloying elements, Ni, Mo, Cr, V and W, into AISI 52100 bearing steel surfaces. Such implantation changes the chemical composition of the steel surface but has relatively little effect on its mechanical properties or topography. The behaviour of zinc dialkyldithiophosphate (ZDDP) antiwear additive was studied. The study employs a ball on disc tribometer with ability to monitor tribofilm development and a range of analytical tools including STEM-EDX, XPS and FIB-TEM to analyse the formed tribofilms. It was found that Ni implantation promotes ZDDP tribofilm formation while Mo and Cr implantation deters tribofilm growth. V and W implantation do not significantly change tribofilm formation. Results on the influence of ZDDP concentration on tribofilm formation rate with different implanted metals suggest that one important mechanism by which steel composition influences tribofilm formation may be by controlling the extent of ZDDP adsorption. This study shows the importance of steel surface composition on ZDDP response and also demonstrates a powerful way to study and potentially improve the tribological performance of machine components via a combination of lubricant formulation and surface modification.

Differences in nano-topography and tribochemistry of ZDDP tribofilms from variations in contact configuration with steel and DLC surfaces

In this work, we evaluated the effect of the counter-body material (the same or dissimilar) and contact configuration (moving or stationary body), at similar contact tribological conditions, on the tribochemical and nanotopography characteristics of adsorbed surface films. Zinc dialkyldithiophosphate (ZDDP), the best performing anti-wear additive, was used in self-mated steel/steel and DLC/DLC contacts, which were compared with mixed steel/DLC and DLC/steel contacts in 1-h and 6-h sliding tests. The macroscale (tribometer) and nanoscale (atomic force microscopy) friction, thickness, topography, and chemical (attenuated total reflection-Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy) properties of the tribofilms were studied. The results revealed unexpectedly large differences in all the studied tribofilm parameters; this is because all the tribofilms are completely different; this includes the chemical composition, which is known to have a crucial effect on the nano- and macro-scale tribological properties. These results clearly demonstrate that the surface material, additives, and common contact operating parameters, that is, pressure, velocity, and temperature, crucially affect the ZDDP tribofilm as well as the position of the moving or stationary surface within the contact, and the material of the moving/stationary bodies.

Synergistic and Competitive Effects between Zinc Dialkyldithiophosphates and Modern Generation of Additives in Engine Oil

The increasing demand for low-viscosity engine oil has underscored the role of zinc dialkyldithiophosphates (ZDDP) as a conventional anti-wear and antioxidant additive. It is essential to investigate the influence of modern additives such as cyclopropanecarboxylic acid (CPCa) and Ni nanoparticles on the tribological performance of ZDDP for practical commercial oil application. According to the experimental results, Ni nanoparticles formed a protective film that exhibited a synergistic effect with ZDDP. A significantly higher concentration of sulphur in the tribofilm was detected compared to ZDDP by itself, which was responsible for a 27.6% lower wear loss. Meanwhile, a competitive effect between CPCa and ZDDP resulted in a dramatic increase in friction and unstable anti-wear performance. This was demonstrated by a localized formation of the ZDDP tribofilm on the wear surfaces after the friction test. These results have highlighted the synergistic and competitive effects of emerging additives (CPCa and Ni nanoparticles) in the ZDDP tribofilm formation between the sliding steel contacts. This further suggests a new approach to increase the efficiency of ZDDP’s tribological performance at cold start-up processes.

Use of XANES and XPS to investigate the effects of ethanol contamination on anti-wear ZDDP tribofilms

This work uses synchrotron radiation XANES and XPS measurements to investigate the structure of ZDDP tribofilms formed from lubricants contaminated with anhydrous and hydrated ethanol (5%wt). The tribofilms were formed at 40 °C from PAO8 lubricant containing only ZDDP additive onto carbon steel specimens using sliding tests, cylinder-on-flat configuration (line contact) under boundary lubrication. Ethanol increased friction as well as surface damage, detected by an increase in relative porous area. Angle-resolved measurements (15°, 45°, 90°) helped detecting differences along the thickness of the tribofilm. The amount of long-chain phosphates apparently reduced with ethanol, leading to reduced wear performance. The sulphides in the tribofilms were richer in Fe in the presence of ethanol, also indicative of more severe wear.

Correction to: Boundary Friction of ZDDP Tribofilms

The original version of this article unfortunately contained a formatting mistake in tables and figures placement.

Tribological Properties of Ti-Doped Diamond-Like Carbon Coatings Under Boundary Lubrication With ZDDP

Abstract Diamond-like carbon (DLC) coatings containing 0.7%, 5.8%, and 23.3% Ti were deposited via pulsed cathodic arc deposition and magnetron sputtering on AISI 316L stainless steel substrates. The varied Ti content was controlled by setting Ti target current at 3, 5, and 7A. The composition, microstructure, mechanical, and tribological properties of Ti-doped DLC (Ti-DLC) coatings were investigated using X-ray photoelectron spectroscopy, Raman spectroscopy, nanoindentation, and ball-on-disc tribometer. The results show that TiC formed when Ti content in the coating was higher than 5.8 at% and the ID/IG ratios increased gradually with the increasing Ti content. Ti-DLC with 0.7 at% Ti had the highest H/E and H3/E2 ratios and exhibited optimal tribological properties under lubrication, especially when zinc dialkyldithio-phosphate (ZDDP) was contained in the oil. Furthermore, ZDDP tribofilms played an important role in wear reduction by protecting the rubbing surfaces against the adhesion and suppressing the tribo-induced graphitization of DLC coatings.

Modeling of Formation and Removal of ZDDP Tribofilm on Rough Surfaces

Zinc dialkyldithiophosphate (ZDDP) is a widely used lubricant additive due to its high effectiveness in reducing wear by forming a tribofilm on sliding surfaces. However, the formation and removal of tribofilm are two competing processes depending on the working conditions, and ZDDP loses its anti-wear function when the removal process prevails. In this paper, a numerical model is built up to predict if ZDDP tribofilm can cover the sliding surfaces and protect them from wear. The input of this model includes the morphology of two sliding surfaces and parameters related to the surface materials, the working conditions and the lubricant, and the output is the surface with tribofilm and/or wear. Then, this model is used for the cylinder liner surface of an internal combustion engine, and a modeling result matching the actual case is obtained, proving that this model can be used in the design of an efficient lubrication system by searching the optimum combination of various parameters. Additionally, it is found that the resolution of the input surfaces has an impact on the modeling result, indicating that caution should be taken when comparing surfaces with different resolutions.