Wetting in a phase separating polymer blend film: quench depth dependence

Abstract

We have used 3He nuclear reaction analysis to measure the growth of the wetting layer as a function of immiscibility (quench depth) in blends of deuterated polystyrene and poly(alpha-methylstyrene) undergoing surface-directed spinodal decomposition. We are able to identify three different laws for the surface layer growth with time t. For the deepest quenches, the forces driving phase separation dominate (high thermal noise) and the surface layer grows with a t(1/3) coarsening behavior. For shallower quenches, a logarithmic behavior is observed, indicative of a low noise system. The crossover from logarithmic growth to t(1/3) behavior is close to where a wetting transition should occur. We also discuss the possibility of a "plating transition" extending complete wetting to deeper quenches by comparing the surface field with thermal noise. For the shallowest quench, a critical blend exhibits a t(1/2) behavior. We believe this surface layer growth is driven by the curvature of domains at the surface and shows how the wetting layer forms in the absence of thermal noise. This suggestion is reinforced by a slower growth at later times, indicating that the surface domains have coalesced. Atomic force microscopy measurements in each of the different regimes further support the above. The surface in the region of t(1/3) growth is initially somewhat rougher than that in the regime of logarithmic growth, indicating the existence of droplets at the surface.