Entropy-induced Microphase Separation in Hard Diblock Copolymers

TL;DR

This paper develops a density functional theory to analyze entropy-driven microphase separation in diblock copolymers composed of hard rods, revealing conditions under which microphase separation occurs before nematic ordering.

Contribution

It introduces an analytical approach for predicting entropy-induced microphase separation in hard diblock copolymers, including a Gaussian limit for long chains, and maps phase diagrams.

Findings

Microphase separation preempts nematic phase for very long chains.

Phase diagrams depend on diameter difference, composition, and segment length ratio.

The Gaussian limit simplifies analysis and predicts phase behavior accurately.

Abstract

Whereas entropy can induce phase behavior that is as rich as seen in energetic systems, microphase separation remains a very rare phenomenon in entropic systems. In this paper, we present a density functional approach to study the possibility of entropy-driven microphase separation in diblock copolymers. Our model system consists of copolymers composed of freely-jointed slender hard rods. The two types of monomeric segments have comparable lengths, but a significantly different diameter, the latter difference providing the driving force for the phase separation. At the same time these systems can also exhibit liquid crystalline phases. We treat this system in the appropriate generalization of the Onsager approximation to chain-like particles. Using a linear stability (bifurcation) analysis, we analytically determine the onset of the microseparated and the nematic phases for long chains. We find that for very long chains the microseparated phase always preempts the nematic. In the limit of infinitely long chains, the correlations within the chain become Gaussian and the approach becomes exact. This allows us to define a Gaussian limit in which the theory strongly simplifies and the competition between microphase separation and liquid crystal formation can be studied essentially analytically. Our main results are phase diagrams as a function of the effective diameter difference, the segment composition and the length ratio of the segments. We also determine the amplitude of the positional order as a function of position along the chain at the onset of the microphase separation instability. Finally, we give suggestions as to how this type of entropy-induced microphase separation could be observed experimentally.