Effects of Ion-Induced Cross-Linking on the Phase Behavior in Salt-Doped Polymer Blends

Abstract

Taking PEO/PS polymer blends doped with lithium salt as example, we study the effects of cross-linking of the EO segments by the Li+ ions on the phase behavior. Combining the Flory–Huggins theory with a statistical model accounting for the combinatorics in forming the cross-links and accounting for the charge neutrality due to the presence of anions, we find an entropic driving force that favors phase separation when the number of EO segments coordinating an Li+ ion exceeds 2. As a result of the asymmetric interaction between the ions and the two polymers, the phase diagram in the polymer composition becomes asymmetric upon addition of the lithium salts. In addition, we examine the effects of preferential solvation energy of the ions which has been shown previously to lead to an increase in the effective χ parameter between the two polymers. We find that the magnitudes of these two driving forces are comparable, but their effects are nonadditive.