Formation of breath figure arrays in methanol vapor assisted by surface active agents

Breath figure (BF) process is a promising technique for fabricating honeycomb polymer films. It is usually conducted in water vapor. While, in organic vapors only unique polymer can be used to prepare BF arrays as reported in our previous article (Breath Figure in Nonaqueous Vapor. Soft Matter, 2013, 506-514), although new structure features are induced in the film. In this paper, a universal modified BF processing is devised for preparing porous films in methanol vapor with conventional polymers, by adding a small amount of surface active agent into the casting solution, such as siloxane- and fluorine-containing block copolymers. The pores in the PS films prepared with this method are of cylindrical shape with large depth-diameter aspect ratio, and the diameter and depth of pores can be well controlled by the experiment conditions. Based on these results, the formation mechanism of honeycomb structure in methanol vapor is discussed.