Crystallinelike Ordering of Confined Liquids at the Moving Contact Line

The friction between a liquid swollen soft elastomer and a solid surface depends on the state of a confined liquid. To measure the physical state of the confined liquid, an interface-sensitive sum frequency generation spectroscopy technique was used to probe the contact region. We find that during sliding (friction) and pull-off (adhesion) experiments of pentadecane-swollen poly(dimethyl siloxane) lenses submerged in linear alkane (pentadecane) on a sapphire substrate, crystallinelike ordering of the liquid occurs only at the contact line, where we anticipate the highest shear. This crystallinelike structure of pentadecane molecules is transient and shows Arrhenius temperature dependence with unusually long relaxation times (hundreds of seconds) and an activation energy (50  kJ/mole), which is twice that of the bulk pentadecane liquid, at temperatures that are 14-70 °C higher than the bulk melting temperature (T_{m}=9 °C). This unusual long-lived crystallinelike ordering may explain why these systems show higher friction coefficients (boundary lubrication) compared to values predicted using bulk viscosity of pentadecane (hydrodynamic lubrication).