Wetting-layer formation mechanisms of surface-directed phase separation under different quench depths with off-critical compositions in polymer binary mixture

Focusing on the off-critical condition, the quench depth dependence of surface-directed phase separation in the polymer binary mixture is numerically investigated by combination of the Cahn-Hilliard-Cook theory and the Flory-Huggins-de Gennes theory. Two distinct situations, i.e., for the wetting, the minority component is preferred by the surface and the majority component is preferred by the surface, are discussed in detail. The simulated results show that the formation mechanism of the wetting layer is affected by both the quench depth and the off-critical extent. Moreover, a diagram, illustrating the formation mechanisms of the wetting layer with various quench depths and compositions, is obtained on the basis of the simulated results. It is found that, when the minority component is preferred by the surface, the growth of the wetting layer can exhibit pure diffusion limited growth law, logarithmic growth law, and Lifshitz-Slyozov growth law. However, when the majority component is preferred by the surface, the wetting layer always grows logarithmically, regardless of the quench depth and the off-critical extent. It is interesting that the surface-induced nucleation can be observed in this case. The simulated results demonstrate that the surface-induced nucleation only occurs below a certain value of the quench depth, and a detailed range about it is calculated and indicated. Furthermore, the formation mechanisms of the wetting layer are theoretically analyzed in depth by the chemical potential gradient. (c) 2007 American Institute of Physics.