The effect of selective surface interaction on polymer phase separation with explicit polydispersity during polymerization.

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In polymerization-induced phase separation, the impact of polymer-substrate interaction on the dynamics of phase separation for polymer blends is important in determining the final morphology and properties of polymer materials as the surface can act as another driving force for phase separation other than polymerization. We modify the previously-developed polymerizing Cahn-Hilliard (pCH) method by adding a surface potential to model the phase separation behavior of a mixture of two species independently undergoing linear step-growth polymerization in the presence of a surface. In our approach, we explicitly model polydispersity by separately considering different molecular-weight components with their own respective diffusion constants, and with the surface potential preferentially acting on only one species. We first show that the surface potential induces faster phase separation of smaller molecules at early stages before the degree of polymerization becomes large enough to drive bulk phase separation. This model is then used to investigate the degree of anisotropic ordering in a direction perpendicular to the surface over various polymerization rates k̃ and strengths of the potential Ṽ. We find that at low k̃, smaller molecules have sufficient time to diffuse and accumulate at the potential surface, resulting in richer production of heavier polymers at the surface without the need for larger polymers to diffuse on their own toward the surface. Conversely, at high k̃, larger polymers first evenly accumulate throughout the system before undergoing phase separation; the concentration wave initiated from the potential surface then propagates into the bulk, resulting in anisotropic phase separation.