Distribution of Interactions in Binary Polymer Mixtures: A Monte Carlo Simulation Study

Phase transitions from miscibility to immiscibility were observed in simulations of binary polymer mixtures on a planar square lattice using reptation sampling techniques. The relationship between the phenomenological interaction parameter, x, and the true molecular interaction energy was followed, and the dependence of the number and distribution of heterocontacts in the mixture on the applied heterosegment interaction energy was determined. Deviations from the results of mean-field treatments, which overestimate the number of heterocontact.s, were observed even for athermal mixtures. Kinetically driven hysteresis governed by a temperature equilibration time scale was examined for the phase transitions. An important prediction of expansion of the polymer chains in the miscibility region can be made on the basis of the results of chain end-to-end distance calculations