Hierarchical self-assembled structure and frictional response of phthalocyanine molecules

Solid evidence is needed to demonstrate the effect of molecular orientation and structure on the frictional property of boundary lubricants.In this work,the frictional properties of phthalocyanine self-assembled monolayers(SAMs)with face-on(aromatic cores parallel to the substrate)and edge-on(aromatic cores stand on the substrate)orientations have been compared and the in situ structural variation of edge-on SAMs under frictional shear has been revealed by atomic force microscope(AFM).Face-on oriented SAMs show lower adhesion,lower friction,and stronger wear resistance,compared with edge-on oriented SAMs.Hierarchical structures of edge-on oriented SAMs have been revealed by frictional topography,which are consisted of nanoscale columns,micron-scale stripes,and centimeter-scale monolayer.The column structure deforms under increasing load force,leading to a stepwise friction force curve and a transition among three friction states(ordered friction,collapsed friction,and worn friction).The structural deformation depends on both the order degree and anisotropic stiffness of columns.Columns in phthalocyanine SAMs show a larger stiffness when shearing against molecular plane than shearing along the molecular plane.The presented study on the interfacial structure and frictional mechanism promisingly supports the designing of novel boundary lubricants and their application in engineering.

Molecular behaviors in thin film lubrication——Part one: Film formation for different polarities of molecules

There are three unsolved problems in thin film lubrication(TFL) since it was proposed 20 years ago, i.e., the determination of the type of molecules that can enter the contact region efficiently during sliding, the orientation of molecules in the contact region, and the effect of solid surfaces on the liquid molecular orientation in TFL. In order to answer the first two questions, an in situ measurement system comprising a self-designed Raman microscopy and relative optical interference intensity(ROⅡ) system was set up to study the molecular behaviors. A variety of binary mixtures were used as lubricants in the test, and the concentration distribution profile and orientation of the additive molecules in TFL were characterized. The molecular behavior was determined via a combination of shearing, confinement, and surface adsorption. Furthermore, the difference in molecular polarity resulted in different competing effect of surface adsorption and intermolecular interaction, the influence of which on molecular behavior was discussed. Polar additive molecules interacted with the steel surface and exhibited an enrichment effect in the Hertz contact region when added into a nonpolar base oil. No enrichment effect was observed for nonpolar molecules that were added into the nonpolar base oil and polar molecules added into polar base oil. The enrichment of additive molecules enhanced the film-forming ability of the lubricant and resulted in a reduction in the friction coefficient of up to 61%. The orderly arrangement of the additive molecules was another reason for the friction-reducing. A binary multilayer model was proposed to illuminate the molecular behavior in the TFL, and the model was supported by contrary experiment results in elastohydrodynamic lubrication. This research may aid in understanding the nanoscale lubrication mechanism in TFL and the development of novel liquid lubricants.