Crystallization of Diblock Copolymer from Microphase Separated Melt

TL;DR

This study uses simulations to explore how thermal annealing influences the crystallization and morphology of microphase separated diblock copolymer melts, revealing effects on crystallization rate, morphology stability, and lamellar structure.

Contribution

It provides new insights into how annealing alters microphase morphology and crystallization behavior in diblock copolymer melts, which was not thoroughly understood before.

Findings

Annealing reorients melt morphology and remains stable during crystallization.

Crystallization rate increases with annealing due to relaxed structure.

Higher B-block content leads to thicker A-block crystals.

Abstract

Diblock copolymers by virtue of the chemical dissimilarity between the constituting blocks exhibit microphase separation in the melt state. The phase separated melt can successfully be exploited to control the morphology of the final semi crystalline materials by allowing an extended thermal annealing. Thermal annealing accelerates coalescence of microdomains, yielding a phase separated melt that would exhibit a distinctly different crystallization behaviour than microphase separated melt without annealing. In this paper, we report simulation results on the crystallization behavior of A-B diblock copolymer, wherein the melting temperature of A-block is higher than B-block, instigated from microphase separated melt. During crystallization, the morphological evolution of microphase separated melt is extensively driven by thermal history. Annealing of microphase separated melt at high temperature successfully reorients melt morphology, and remains almost unaltered during the subsequent crystallization (isothermal and non-isothermal), which is attributed to the hard confinement resulted during microphase separation. Annealing induces a change in bond orientation of A-block, whereas there is no appreciable change in bond orientation of B-block keeping crystallinity and lamellar thickness unaffected. Isothermal crystallization confines crystallization in phase separated microdomain whereas non-isothermal crystallization results in morphological perturbation. The crystallization rate of annealed melt is much faster than the non-annealed melt due to less entanglement and more relaxed structure, achieved via annealing. At a higher composition of B-block, A-block produces thicker crystals, which is attributed to the dilution effect exhibited by B-block. Two-step compared to one-step isothermal crystallization yields thicker crystals with higher crystallinity of A-block.