LCST and Closed-Loop Phase Behavior in Non-Associating Fully Symmetric Multicomponent Polymer Systems

Abstract: Multicomponent liquids can phase separate upon heating, exhibiting a lower critical solution temperature (LCST). Moreover, a narrow class of materials can undergo disordering transition upon further heating, yielding closed-loop phase diagrams. Previously, it was shown that LCST or closed-loop phase behavior can appear in the models of liquids in which components are asymmetric or interaction potentials have a specifically designed attraction. Here, we show theoretically that LCST and closed-loop phase behavior can occur in a significantly wider set of models. In particular, we found that these phenomena can be exhibited by the simplest and widely used coarse-grained (CG) models of any multicomponent liquid in which species are fully symmetric and where all particles interact via an arbitrary repulsive potential. In addition, we discovered that LCST and closed-loop phase behavior in these models emerges merely due to the basic property of CG liquid models, namely, the appearance of strong monomer-monomer positional correlations at low monomer number density $ρ$. We simulated the models of fully symmetric binary blends and diblock copolymer melts where nonbonded monomers interacted via a generic T-independent purely repulsive harmonic potential. As predicted, LCST and closed-loop phase behavior emerged at $ρ$ sufficiently low to cause strong monomer-monomer correlations leading to a strong T-dependence of the effective coordination number, which, in turn, induced a nonmonotonic T-dependence of the Flory-Huggins parameter. To summarize, we discovered that the simplest fully symmetric non-associating CG models of multicomponent liquids can exhibit complex temperature response due to a mechanism stemming from the basic nature of any CG liquid model. This mechanism might contribute to the emergence of LCST and closed-loop phase behavior in many existing polymer materials.