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arXiv · 1905.01717

Phase Behavior of Melts of Diblock-Copolymers with One Charged Block

Alexey A. Gavrilov·Alexander V. Chertovich·Igor I. Potemkin
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Abstract

In this work we investigated the phase behavior of melts of block-copolymers with one charged block by means of dissipative particle dynamics with explicit electrostatic interactions. We assumed that all the Flory-Huggins \c{hi} parameters were equal to 0 and showed that the charge correlation attraction solely can cause microphase separation with long-range order; a phase diagram was constructed by varying the volume fraction of the uncharged block and the electrostatic interaction parameter {\lambda}. The obtained phase diagram was compared to the phase diagram of corresponding neutral diblock-copolymers. Surprisingly, the differences between these phase diagrams are rather subtle; the same phases are observed, and the positions of the ODT points are similar if the {\lambda}-parameter is considered as an "effective" \c{hi}-parameter. Next, we studied the position of the ODT for lamellar structure depending on the chain length N. It turned out that while for the uncharged diblock-copolymer the product \c{hi}crN was almost independent of N, for the diblock-copolymers with one charged block we observed a significant increase in {\lambda}crN upon increasing N. It can be attributed to the fact that the counterion entropy prevents the formation of ordered structures. This was supported by studying the ODT in diblock-copolymers with charged blocks and counterions cross-linked to the charged monomer units. The ODT for such systems was observed at significantly lower values of {\lambda} with the difference being more pronounced at longer chain lengths N. The diffusion of counterions in the obtained ordered structures was studied and compared to the case of a system with the same number of charged groups but homogeneous structure; the diffusion coefficient in a direction in the lamellar plane was found to be higher than in any direction in homogeneous structure.

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Alexey A. Gavrilov, Alexander V. Chertovich, Igor I. Potemkin. 2019-05-05. Phase Behavior of Melts of Diblock-Copolymers with One Charged Block. https://doi.org/10.3390/polym11061027

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