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.

Zinc dialkyldithiophosphate (ZDDP) is added to engine lubricants to reduce wear and ensure reliable operation. ZDDP reacts under rubbing conditions to form protective zinc/iron phosphate tribofilms on steel surfaces. Recently, it has been demonstrated that this process can be promoted by applied stresses in lubricated contacts, as well as temperature, and is thus mechanochemical in origin. In this study, a tribology test rig capable of applying very high loads has been developed to generate ZDDP tribofilms under full-film elastohydrodynamic lubrication (EHL) conditions in steel/steel ball-on-disk contacts. This provides a well-defined temperature and stress environment with negligible direct asperity contact in which to study mechanochemical processes. ZDDPs with branched primary and secondary alkyl substituents have been studied in three base oils, two with high EHL friction and one with low EHL friction. In the high EHL friction base oils, the tribofilm growth rate increases exponentially with shear stress and temperature for both ZDDPs, as predicted by a stress augmented thermal activation model. Conversely, under otherwise identical conditions, negligible ZDDP tribofilm formation takes place in the low EHL friction base oil. This confirms that the ZDDP reaction is driven by macroscopic shear stress rather than hydrostatic pressure. The secondary ZDDP forms tribofilms considerably faster than the primary ZDDP under equivalent conditions, suggesting that the initial decomposition reaction is the rate determining step for tribofilm formation. The rate of tribofilm growth is independent of ZDDP concentration over the range studied, indicating that this process follows zero-order kinetics. Under full-film EHL conditions, ZDDP tribofilm formation is promoted by macroscopic shear stress applied through the base oil molecules, which induces asymmetric stress on adsorbed ZDDP molecules to promote their decomposition and initiate rapid phosphate polymerisation.

There is currently considerable debate concerning the most appropriate rheological model to describe the behaviour of lubricant films in rolling-sliding, elastohydrodynamic contacts. This is an important issue since an accurate model is required in to predict friction in such contacts. This paper reviews the origins of this debate, which primarily concerns a divergence of views between researchers using high pressure, high shear rate viscometry and those concerned with the measurement and analysis of elastohydrodynamic friction; the former advocate a Carreau-based shear stress/strain rate model while the latter generally favour an Eyring-based one. The crucial importance of accounting for shear heating effects in analysing both viscometric and friction data is discussed. The main criticisms levied by advocates of a Carreau-based model against Eyring's model are discussed in some detail. Finally the ability of both types of rheological model to fit elastohydrodynamic friction measurements for a quite simple, well-defined base fluid is tested, using previously-measured pressure-viscosity behaviour for the fluid. Both models appear to fit the experimental data over a wide temperature range quite well, though fit of the Eyring model appears slightly closer than that of the Carreau-Yasuda model. Friction data from a wider range of welldefined fluid types is needed to identify categorically the most appropriate model to describe elastohydrodynamic friction.

The EHD friction properties of a wide range of base fluids have been measured and compared in mixed sliding-rolling conditions at three temperatures and two pressures. The use of tungsten carbide ball and disc specimens enabled high mean contact pressures of 1.5 and 2.0 GPa to be obtained, comparable to those present in many rolling bearings. The measurements confirm the importance of molecular structure of the base fluid in determining EHD friction. Liquids having linear-shaped molecules with flexible bonds give considerably lower friction than liquids based on molecules with bulky side groups or rings. EHD friction also increases with viscosity for liquids having similar molecular structures. Using pure ester fluids, it is shown that quite small differences in molecular structure can have considerable effects on EHD friction. The importance of temperature rise in reducing EHD friction at slide-roll ratios above about 5% has been shown. By measuring EHD friction at several temperatures and pressures as well as EHD film thickness, approximate corrections to measured EHD friction data have been made to obtain isothermal shear stress and thus EHD friction curves. These show that under the conditions tested most low molecular weight base fluids do not reach a limiting friction coefficient and thus shear stress. However, two high traction base fluids appear to reach limiting values, while three linear polymeric base fluids may also do so. Constants of best fit to a linear/logarithmic isothermal shear stress/strain rate relationship have been provided to enable reconstruction of isothermal EHD friction behaviour for most of the fluids tested.

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Beneath ultraslow‐spreading ridges, the oceanic lithosphere remains poorly understood. Using recordings from a temporary array of ocean bottom seismometers, we here report an ~17‐days‐long microearthquake study on two segments (27 and 28) of the ultraslow‐spreading Southwest Indian Ridge (49.2° to 50.8°E). A total of 214 locatable microearthquakes are recorded; seismic activity appears to be concentrated within the west median valley at Segment 28 and adjacent nontransform discontinuities. Earthquakes reach a maximum depth of ~20 km beneath the seafloor, and they mainly occur in the mantle, implying a cold and thick brittle lithosphere. The relatively uniform brittle/ductile boundary beneath Segment 28 suggests that there is no focused melting in this region. The majority of earthquakes is located below the Moho interface, and a 5‐km‐thick aseismic zone is present beneath Segment 28 and adjacent nontransform discontinuities. At the Dragon Flag hydrothermal vent field along Segment 28, the presence of a detachment fault has been inferred from geomorphic features and seismic tomography. Our seismicity data show that this detachment fault deeply penetrates into the mantle with a steeply dipping (~65°) interface, and it appears to rotate to a lower angle in the upper crust, with ~55° of rollover. There is a virtual seismic gap beneath magmatic Segment 27, which may be connected to the presence of an axial magma chamber beneath the spreading center and focused melting; in this scenario, the increased magma supply produces a broad, elevated temperature environment, which suppresses earthquake generation.

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The frictional properties of ZDDP tribofilms at low entrainment speeds in boundary lubrication conditions have been studied in both rolling/sliding and pure sliding contacts. It has been found that the boundary friction coefficients of these tribofilms depend on the alkyl structure of the ZDDPs. For primary ZDDPs, those with linear alkyl chains give lower friction those with branched alkyl chain ZDDPs, and a cyclohexylmethyl-based ZDDP gives markedly higher friction than non-cyclic ones. Depending on alkyl structure, boundary friction coefficient in rolling-sliding conditions can range from 0.09 to 0.14. These differences persist over long duration tests lasting up to 120 h. For secondary ZDDPs, boundary friction appears to depend less strongly on alkyl structure and in rolling-sliding conditions stabilises at ca 0.115 for the three ZDDPs studied. Experiments in which the ZDDP-containing lubricant is changed after tribofilm formation by a different ZDDP solution or a base oil indicate that the characteristic friction of the initial ZDDP tribofilm is lost almost as soon as rubbing commences in the new lubricant. The boundary friction rapidly stabilises at the characteristic boundary friction of the replacement ZDDP, or in the case of base oil, a value of ca 0.115 which is believed to represent the shear strength of the bare polyphosphate surface. The single exception is when a solution containing a cyclohexylethyl-based ZDDP is replaced by base oil, where the boundary friction coefficient remains at the high value characteristic of this ZDDP despite the fact that rubbing in base oil removes about 20 nm of the tribofilm. XPS analysis of the residual tribofilm reveals that this originates from presence of a considerable proportion of C-O bonds at the exposed tribofilm surface, indicating that not all of the alkoxy groups are lost from the polyphosphate during tribofilm formation. Very slow speed rubbing tests at low temperature show that the ZDDP solutions give boundary friction values that vary with alkyl group structure in a similar fashion to rolling-sliding MTM tests. These variations in friction occur immediately on rubbing, before any measurable tribofilm can develop. This study suggest that ZDDPs control boundary friction by adsorbing on rubbing steel or tribofilm surfaces in a fashion similar to organic friction modifiers. However it is believed that, for primary ZDDPs, residual alkoxy groups still chemically bonded to the phosphorus atoms of newly-formed polyphosphate/phosphate tribofilm may also contribute to boundary friction. This understanding will contribute to the design of low friction, fuel efficient crankcase engine oils. Graphical Abstract