Solvent and substrate contributions to the formation of breath figure patterns in polystyrene films

The generation of ordered porous polymer structures by the breath figures (BFs) method has long been described as a complex phenomenon, in which several parameters combine in a fairly unknown way. The type of polymer and solvent, degree of humidity, and additives are just a few examples of the several parameters that have been described as playing a role in the generation of BFs. This work reports a detailed investigation over the role played by the solvent in the process of BFs generation from polystyrene (PS) solutions spread over different substrates, and discusses the geometrical aspects of the pores via a quantitative point of view by using a purposely developed software for image analysis. Results show that thermodynamic affinity between polymer and solvent is the key parameter for BFs formation, along with other solvent characteristics such as water miscibility, boiling point, and enthalpy. According to our findings, the role played by the substrate is strictly related to the type of solvent used in the generation of BFs.