Substituent effects on the mechanochemical response of zinc dialkyldithiophosphate

Mechanochemistry is known to play a key role in the function of some lubricant additives, such as the tribofilm growth of zinc dialkyldithiophosphate (ZDDP). This raises the intriguing possibility of tailoring the mechanochemical response of additives by modifying their alkyl substituents. Here, we study the tribofilm formation rate of ZDDPs containing several different alkyl groups on steel surfaces from a high-friction base oil. We use macroscale tribometer experiments under full-film elastohydrodynamic lubrication conditions to enable careful control of the temperature and stress during tribofilm growth. We show how the chain length and the presence of branches or bulky cycloaliphatic groups can lead to large differences in the temperature- and stress-dependencies of the tribofilm formation rate, which can be explained through variations in packing density, steric hindrance, and stress transmission efficiency. Our rate data are successfully fitted using the Bell model; a simple modification of the Arrhenius equation that is commonly employed to model the kinetics of mechanochemical processes. Using this model, we observe large differences in the activation energy, pre-exponential factor, and activation volume for the various ZDDPs. Our findings show how structure–performance relationships can be identified for lubricant additives, which may be useful to optimise their molecular structure

Thermal conductivity and flash temperature

The thermal conductivity is a key property in determining the friction-induced temperature rise on the surface of sliding components. In this study, a Frequency Domain Thermoreflectance (FDTR) method is used to measure the thermal conductivity of a range of tribological materials (AISI 52100 bearing steel, silicon nitride, sapphire, tungsten carbide and zirconia). The FDTR technique is validated by comparing measurements of pure germanium and silicon with well-known values, showing discrepancies of less than 3%. For most of the tribological materials studied, the thermal conductivity values measured are reasonably consistent with values found in the literature. However the measured thermal conductivity of AISI 52100 steel (21 W/mK) is less than half the value cited in the literature (46 W/mK). Further bulk thermal conductivity measurements show that this discrepancy arises from a reduction in thermal conductivity of AISI 52100 due to through-hardening. The thermal conductivity value generally cited and used in the literature represents that of soft, annealed alloy, but through-hardened AISI 52100, which is generally employed in rolling bearings and for lubricant testing, appears to have a much lower thermal conductivity. This difference has a large effect on estimates of flash temperature and example calculations show that it increases the resulting surface temperatures by 30 to 50%. The revised value of thermal conductivity of bearing steel also has implications concerning heat transfer in transmissions

Effect of base oil structure on 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

Tribofilm formation, friction and wear-reducing properties of some phosphorus-containing antiwear additives

The film-forming, friction and wear properties of a range of model and commercial ashless P and P/S antiwear additives have been studied. A method has been developed for removing the tribofilms formed by such additives in order to effectively quantify mild wear. In general the P/S additives studied formed thinner tribofilms but gave lower wear than the S-free P ones. In extended wear tests, three P/S additives gave wear as low, or lower, than a primary zinc dialkyldithiophosphate (ZDDP). For almost all lubricants tested the wear rate measured in short tests was considerably higher than that in long tests due to the greater contribution of running-in wear in the former. This highlights the importance of basing antiwear additive choice on reasonably long tests, where running-in becomes only a small component of the wear measured. It has been found that for both P and P/S ashless additives the addition of oil-soluble metal compounds based on Ti and Ca boosts tribofilm formation and can lead to very thick films, comparable to those formed by ZDDP. However, this thick film formation tends to be accompanied by an increase in mixed friction and also does not appear to reduce wear but may even increase it

Correlation of elastohydrodynamic friction with molecular structure of highly refined hydrocarbon base oils

The molecular compositions of a range of low viscosity hydrocarbon base oils spanning API Groups II to IV have been quantified using 13C NMR and correlated with base oil elastohydrodynamic (EHD) friction. A strong correlation has been found between the proportions of paraffin, linear and branched carbons and EHD friction, with a high proportion of linear and paraffinic carbon atoms contributing to low-EHD friction but branched carbons contributing to high-EHD friction. Correlation equations have been developed to predict EHD friction based on base oil composition. At very high temperature and low pressure, this correlation breaks down as the lubricant in the contact does not reach sufficiently high shear stress for shear thinning to occur. For Group IV polyalphaolefin, the correlation must be extended to account for the very high proportion of linear carbons originating from linear alkene oligomerization. The correlations developed in this study can be used to guide the design of low-EHD friction base oils