Friction and wear are important technologically. Tires on wet roads, windshield wipers and human joints are examples where nanometer-thick liquids are confined between flexible-rigid contact interfaces. Fundamental understanding of the structure of these liquids can assist in the design of products such as artificial joints and lubricants for Micro-electromechanical systems [MEMS]. Prior force measurements have suggested an increase in apparent viscosity of confined liquid and sometimes solid-like responses. But, these have not given the state of molecules under confinement. In the present study, we have used a surface sensitive, non-linear optical technique (infrared-visible sum frequency generation spectroscopy [SFG]) to investigate molecular structure at hidden interfaces. SFG can identify chemical groups, concentration and orientation of molecules at an interface.
A friction cell was developed to study sliding of a smooth elastomeric lens against a sapphire surface. Experiments were done with dry sliding as well as lubricated sliding in the presence of linear alkane liquids. SFG spectra at the alkane / sapphire interface revealed ordering of the confined alkane molecules. These were more ordered than alkane liquid, but less ordered than alkane crystal. Cooling of the confined alkane below its melting temperature [TM] led to molecular orientation that was different from that of bulk crystal next to a sapphire surface. Molecules were oriented with their symmetry axis parallel to the surface normal. In addition, the melting temperature [Tconf] under confinement for a series of linear alkanes (n =15 - 27) showed a surprising trend. Intermediate molecular weights showed melting point depression. The Tconf values suggested that melting started at the alkane / sapphire interface.
In another investigation, confinement of water between an elastomeric PDMS lens and sapphire was studied. SFG spectra at the sapphire / water / PDMS interface revealed a heterogeneous morphology. The presence of peaks related to PDMS, as well as water, suggested water puddles in the contact area and the sapphire surface had a layer of bound water. This heterogeneity picture provides insight into high friction and stick-slip behavior found in boundary lubrication.
For the first time, a broadband SFG system has been coupled with a friction cell to study dynamics and molecular changes at an interface during sliding; sliding of confined alkane between sapphire and PDMS was investigated. A series of SFG spectra were taken while the confined alkane contact spot moved in and out of the laser beam. Even though the experiments were done 15°C above melting temperature, the spectra showed ordering of alkane molecules, similar to that of the confined crystal at the leading and trailing edge. The results suggest that a large portion of the resistance to sliding may come from ordering of molecules at the lens front.