Influence of Succinimide Dispersants on Film Formation, Friction and Antiwear Properties of Zinc Dialkyl Dithiophosphate

ZDDP (zinc dialkyldithiophosphate) is arguably the most successful antiwear additive ever employed in crankcase engine lubricants. It was originally used as an antioxidant and shortly afterwards recognized for its antiwear and extreme pressure properties. Unfortunately, another critical additive polyisobutylsuccinimide-polyamine (PIBSA-PAM), which is used as a dispersant in engine oils, is known to be antagonistic to ZDDP in terms of film formation, friction and wear. The mechanisms of this antagonism have been widely studied, but they are still not well understood. Furthermore, in order to protect engine exhaust catalysts from sulphated ash, phosphorus and sulphur (SAPS) and extend drain intervals of engine lubricants, a progressive reduction in ZDDP quantity but a growth in the use of PIBSA-PAM is required. The aim of this study is to explore the mechanisms and practical effects of the antagonism between ZDDP and PIBSA-PAM. Of particular interest is the impact on performance of the ratio of ZDDP to PIBSA-PAM, as measured by P:N ratio. Since ZDDP is a very effective antiwear additive, it produces only very low or "mild" rates of wear. To study this requires a new way to measure mild wear behaviour of formulated oils. Several techniques have been applied in this study to investigate the film formation, friction and wear properties of ZDDP- and/or PIBSA-PAM-containing oils. These include a new mild wear testing method, which is tested and developed using a range of different types of additives. It is found that the ratio of P:N plays a strong role in determining tribofilm formation and friction of ZDDP/PIBSA-PAM blends. However it plays a much weaker role in determining wear behaviour. It is found that some PIBSA-PAMs have considerable friction-reducing properties in their own right. The results suggest that PIBSA-PAM may interfere with the behaviour of ZDDP in several ways: by forming a ZDDP/ PIBSA-PAM complex at the metal surfaces to reduce the local activity of ZDDP; by PIBSA-PAM partially removing the ZDDP film; possibly also by PIBSA-PAM blocking ZDDP from metal surfaces. The newly-developed wear testing method can be used conveniently and effectively to study mild wear properties not just of ZDDP but of a wide range of other additives

Ion-mediated RNA structural collapse: effect of spatial confinement

RNAs are negatively charged molecules residing in macromolecular crowding cellular environments. Macromolecular confinement can influence the ion effects in RNA folding. In this work, using the recently developed tightly bound ion model for ion fluctuation and correlation, we investigate the confinement effect on the ion-mediated RNA structural collapse for a simple model system. We found that, for both Na$^+$ and Mg$^{2+}$, ion efficiencies in mediating structural collapse/folding are significantly enhanced by the structural confinement. Such an enhancement in the ion efficiency is attributed to the decreased electrostatic free energy difference between the compact conformation ensemble and the (restricted) extended conformation ensemble due to the spatial restriction.Comment: 22 pages, 5 figure