On the mechanism of ZDDP antiwear film formation

Zinc dialkyldithiophosphate additives are used to control wear and inhibit oxidation in almost all engine oils as well as many other types of lubricant. They limit wear primarily by forming a thick, protective, phosphate glass-based tribofilm on rubbing surfaces. This film formation can occur at low temperatures and is relatively indifferent to the chemical nature of the substrate. There has been considerable debate as to what drives ZDDP tribofilm formation, why it occurs only on surfaces that experience sliding and whether film formation is controlled primarily by temperature, pressure, triboemission or some other factor. This paper describes a novel approach to the problem by studying the formation of ZDDP films in full film EHD conditions from two lubricants having very different EHD friction properties. This shows that ZDDP film formation does not require solid-solid rubbing contact but is driven simply by applied shear stress, in accord with a stress-promoted thermal activation model. The shear stress present in a high pressure contact can reduce the thermal activation energy for ZDDP by at least half, greatly increasing the reaction rate. This mechanism explains the origins of many practically important features of ZDDP films; their topography, their thickness and the conditions under which they form. The insights that this study provides should prove valuable both in optimising ZDDP structure and in modelling ZDDP antiwear behaviour. The findings also highlight the importance of mechanochemistry to the behaviour of lubricant additives in general

The influence of slide–roll ratio on ZDDP tribofilm formation

The anti-wear performance and action mecha- nisms of zinc dithiophosphate (ZDDP) have been investi- gated under various test conditions. The Mini Traction Machine–Space Layer Imaging (MTM–SLIM) is a widely used and useful method for monitoring tribofilm formation by ZDDPs. However, tests are generally carried out in mixed sliding–rolling conditions, typically between 50 % SRR (slide–roll ratio) and 100 % SRR. In this paper, the authors describe an investigation of ZDDP film formation at SRRs much higher than 100 % SRR, including pure sliding conditions using a novel MTM–SLIM technique. At high SRRs, ZDDP tribofilms form without damaging the ball surfaces so long as both surfaces move above a threshold speed with respect to the contact, regardless of whether the two surfaces move in the same or opposing directions. In pure sliding conditions, although the worn area expands with time under pure sliding conditions showing that wear takes place, tribofilms are still built up throughout a test and the ZDDP has a beneficial effect on wear rate. The very early stages of film formation are studied to show that a tribofilm with a high concentration of S is formed initially and then replaced with a film having a high concentration of Zn and P

Effect of steel hardness on soot wear

Due to incomplete combustion, high levels of soot can accumulate in engine lubricants between drain intervals. This soot can promote wear of engine parts such as timing chains and cam followers. One standard approach to reducing wear is to increase the hardness of the rubbing components used. According to the Archard wear equation, wear rate should be broadly inversely proportional to hardness. To explore this approach for controlling soot wear, wear tests have been conducted in a High Frequency Reciprocating Rig (HFRR) with HFRR steel discs of various hardness against a hard steel ball. Carbon black (soot surrogate) dispersions in model lubricants based on solutions of ZDDP and dispersant in GTL base oils have been studied. Wear volumes have been measured and wear scars and tribofilms analysed using scanning white light interferometry and SEM-EDS. It is found that, while most oils show wear that reduces with increasing hardness, for blends that contain both ZDDP and carbon black, wear rate markedly increases with disc hardness as the latter approaches the hardness of the ball. The results support the prevalence of a corrosive-abrasive wear mechanism when carbon black and ZDDP are both present in a lubricant and suggests that selection of very hard surfaces may not be a useful way to control soot