Phase-field simulation for the formation of porous microstructures due to phase separation in polymer solutions on substrates with different wettabilities

The porous microstructure has been widely observed in a variety of polymer solutions that have been broadly applied in many industry fields. Phase separation is one of the common mechanisms for the formation of the porous microstructure in binary polymeric mixtures. Previous studies for the formation of porous microstructures mostly focus on the separation of the bulk phase. However, there is a paucity of investigation for the phase separation of polymer mixtures contacting the solid substrate. When the polymeric liquid mixtures interact with the solid substrate, the wetting boundary condition has to be taken into account. In this work, we present a phase-field model which is coupled with the wetting boundary condition to study the phase separation in binary polymer solutions. Our consideration is based on the polymerization-induced phase separation, and thermally induced phase separation by using the Flory-Huggins model. By taking the wetting effect into account, we find that polymer droplets spontaneously occur in the microstructure, even though the bulk composition is outside the spinodal region. This phenomenon is caused by the surface composition resulting from the wetting effect that was often overlooked in literature. For the phase separation in the binary polymer mixture, we also study the impact of the temperature gradient on the microstructural evolution. The porosity, the number of droplets, and the mean radius of the droplets are rationalized with the temperature gradient.