The Effects of Ultra Thin Films on Dynamic Wetting

Dynamic wetting, the displacement of one fluid by another immiscible fluid on a surface, controls many natural and technological phenomena, such as coating, printing, spray painting and lubricating. Particularly in coating and spraying applications, contact lines advance across pre-existing fluid films. Most previous work has focused on contact lines advancing across films sufficiently thick that they behave as simple Newtonian fluids. Ultrathin films, where the film thickness may impinge on fundamental length scales in the fluid, have received less attention. In this talk, we will discuss the effects of ultrathin polymer films on dynamic wetting. We measure the interface shape within microns of moving contact lines advancing across preexisting films and compare the measurements to existing models of viscous bending for interfaces advancing across dry surfaces and 'thick' (in the sense that they behave as liquids) films. In the experiments, we advance a contact line of 10-poise and 1-poise polydimethylsiloxane (silicone oil) across pre-coated films of the same fluid with thickness from a single chain thickness (approx. 10 A) through a couple of radii of gyration (100-200 A) to films so thick they are likely bulk in behavior (10(exp 3) A). All films are physisorbed, i.e. they readily rinse from the surface. Thus, molecules in the film are not anchored to the surface and can move within the film if the hydrodynamics dictate such motion. For films of the thickness of a single chain (approx. 10 A), our experiments indicate that the advancing fluid behaves just as it would if it advanced over a dry surface. For the thicker films (10(exp 3) A), we find behavior indicating that the molecules in the film are acting as a fluid with the bulk properties. In this regime, results for the two different fluids are identical when the experiments are performed at the same pre-existing film thickness and advancing capillary number, Ca. For film of thickness of a few radii of gyration (approx. 100-200 A), the behavior depends on Ca of the advancing meniscus. At low Ca, the viscous bending of the interface near the contact line does not behave as it would on a dry surface. It has a lower curvature than expected. However, at higher Ca, the viscous bending is described by the model for spreading over a dry surface. These results show that the fluid flow in the film does behave differently than bulk as the film thickness becomes comparable to molecular length scale. But even more intriguing is the unusual velocity dependence of that behavior where the film behaves more solid-like at higher contact line speeds. We will discuss these results in terms of the properties of confined polymer melts.