Glasslike Transitions in Thin Polymer-Melt Films Due to Thickness Constraint

The shear properties of thin films of star and linear polyisoprene (PIP) melts under high pressure were investigated as a function of sliding velocity (shear rate) using the surface forces apparatus. The results were contrasted with their bulk rheological properties; effects of thickness constraint on the shear behavior were discussed. The melts of PIP in bulk exhibit Newtonian-like constant viscosity at least at low shear rates (frequencies), which suggests that individual molecules flow with lateral sliding motion. However, thin films of PIP melts show tribological features involving apparent shear-thinning behavior, indicative of the correlated motions in confined geometries. The shear-property change from bulk rheological behavior to thin-film tribological behavior along with the thickness decrease reflects the physical states and their transitions in the systems; the thickness constraint induces glasslike transitions. Effects of molecular weights and molecular architecture (star-branched or linear) on the shear properties are also discussed.     

Modification of Boundary Lubrication by Oil-Soluble Friction Modifier Additives

The molecular-level function of model and commercial friction modifier additives in lubricants of the type used at the wet clutch interface in automatic transmissions has been studied using a surface forces apparatus (SFA) modified for oscillatory shear. The nanorheological properties of tetradecane with and without a model friction modifier additive (1-hexadecylamine) were examined in the boundary lubrication regime and compared to a fully-formulated automatic transmission fluid (ATF). 1-Hexadecylamine adsorbed as a single layer on the sliding surfaces, reduced the static frictional force and the limiting shear stress, and eliminated the stick–slip transition that exists in pure tetradecane. The ATF, which contains commercial-grade friction modifiers, showed nanorheological properties similar to those observed for tetradecane containing 0.1–0.2 wt% 1-hexadecylamine.     

Molecular tribology of lubricants and additives

Knowledge of the bulk viscosity provides little guidance to predict accurately the interfacial shear strength and effective viscosity of a fluid in a lubricated contact. To quantify these differences between bulk and thin-film viscosity, an instrument was developed to measure the shear of parallel single crystal solids separated by molecularly-thin lubricant films. The effective shear viscosity is enhanced compared to the bulk, relaxation times are prolonged, and nonlinear responses set in at lower shear rates. These effects are more prominent, the thinner the liquid film. Studies with lubricant additives cast doubt on the usefulness of the concept of a friction coefficient for lubricated sliding.     

Exploring the “friction modifier” phenomenon: nanorheology of n‐alkane chains with polar terminus dissolved in n‐alkane solvent

Dilute solutions of two polar end‐functionalized linear alkanes (1‐hexadecylamine and palmitic acid), each dissolved in tetradecane, were confined between two mica surfaces and investigated using a surface forces apparatus modified to study shear nanorheology. These two solutions showed similar nanorheological properties that differed from those observed for pure n‐alkanes. In static measurements, a “hard wall”, rather than an oscillatory force, was observed as a function of film thickness. The polar alkane component formed a weakly adsorbed single layer at each mica surface, disrupting the layered structures found in neat n‐tetradecane. In dynamic experiments at low shear amplitude, the storage modulus G' exceeded the loss modulus G" at low frequencies; above some characteristic frequencies G' increased such that g' ≈ G", indicating significantly more energy loss through viscous modes at higher frequency. When the amplitude was varied at fixed frequency, no stick–slip was observed and the limiting value of the shear stress at high effective shear rate was an order of magnitude less than for unfunctionalized n‐alkanes at similar loads. Together, these results show that the addition of a small amount of polar alkane component, by disrupting the layered structures that would have been formed in the neat n‐alkane, is effective in suppressing static friction and reducing kinetic friction in the boundary lubrication regime. This revised version was published online in July 2006 with corrections to the Cover Date.