Random Isotropic Structures and Possible Glass Transitions in Diblock Copolymer Melts

TL;DR

This paper develops a thermodynamic replica approach to study microstructural glass transitions in diblock copolymer melts, revealing how the transition relates to mean-field spinodal behavior and the influence of cubic interactions on phase stability.

Contribution

It introduces a systematic expansion in inverse polymerization degree to analyze glass transitions and includes cubic fluctuation corrections in the ODT, providing new insights into phase stability.

Findings

Glass transition and spinodal collapse in the infinite chain limit.

Cubic interactions stabilize ordered and glassy phases.

Asymmetry can cause glass transition to occur before ordering.

Abstract

We study the microstructural glass transitions in diblock-copolymer melts using a thermodynamic replica approach. Our approach performs an expansion in terms of the natural smallness parameter -- the inverse of the scaled degree of polymerization, which allows us to systematically study the approach to mean-field behavior as the degree of polymerization increases. We find that in the limit of infinite long polymer chains, both the onset of glassiness and the vitrification transition (Kauzmann temperature) collapse to the mean-field spinodal, suggesting that the spinodal can be regarded as the mean-field signature for glass transitions in this class of systems. We also study the order-disorder transitions (ODT) within the same theoretical framework; in particular, we include the leading-order fluctuation corrections due to the cubic interaction in the coarse-grained Hamiltonian, which has been ignored in previous works on the ODT in block copolymers. We find that the cubic term stabilizes both the ordered (body-centered-cubic) phase and the glassy state relative to the disordered phase. While in melts of symmetric copolymers the glass transition always occurs after the order-disorder transition (below the ODT temperature), for asymmetric copolymers, it is possible that the glass transition precedes the ordering transition.