Three-phase coexistence with sequence partitioning in symmetric random block copolymers

TL;DR

This paper investigates the coexistence of macroscopic and microstructured phases in symmetric random block copolymers, revealing complex phase behavior including fractionation and multicritical points, using analytical and numerical methods.

Contribution

It introduces an analytical framework for understanding phase coexistence and fractionation in random block copolymers, extending to multicritical points and comparing with SCFT results.

Findings

Identification of three-phase coexistence regions with fractionation.

Analytical derivation of multiphase free energy accounting for sequence exchange.

Comparison of analytical results with numerical SCFT for Q=3 copolymers.

Abstract

We inquire about the possible coexistence of macroscopic and microstructured phases in random Q-block copolymers built of incompatible monomer types A and B with equal average concentrations. In our microscopic model, one block comprises M identical monomers. The block-type sequence distribution is Markovian and characterized by the correlation \lambda. Upon increasing the incompatibility \chi\ (by decreasing temperature) in the disordered state, the known ordered phases form: for \lambda\ > \lambda_c, two coexisting macroscopic A- and B-rich phases, for \lambda\ < \lambda_c, a microstructured (lamellar) phase with wave number k(\lambda). In addition, we find a fourth region in the \lambda-\chi\ plane where these three phases coexist, with different, non-Markovian sequence distributions (fractionation). Fractionation is revealed by our analytically derived multiphase free energy, which explicitly accounts for the exchange of individual sequences between the coexisting phases. The three-phase region is reached, either, from the macroscopic phases, via a third lamellar phase that is rich in alternating sequences, or, starting from the lamellar state, via two additional homogeneous, homopolymer-enriched phases. These incipient phases emerge with zero volume fraction. The four regions of the phase diagram meet in a multicritical point (\lambda_c, \chi_c), at which A-B segregation vanishes. The analytical method, which for the lamellar phase assumes weak segregation, thus proves reliable particularly in the vicinity of (\lambda_c, \chi_c). For random triblock copolymers, Q=3, we find the character of this point and the critical exponents to change substantially with the number M of monomers per block. The results for Q=3 in the continuous-chain limit M -> \infty are compared to numerical self-consistent field theory (SCFT), which is accurate at larger segregation.