Modulating Microphase Separation of Lamellae-Forming Diblock Copolymers via Ionic Junctions

Wei Li; Jan Michael Y. Carrillo; Bobby G. Sumpter; Rajeev Kumar

doi:10.1021/acsmacrolett.0c00592

Modulating Microphase Separation of Lamellae-Forming Diblock Copolymers via Ionic Junctions

Wei Li, Jan Michael Y. Carrillo, Bobby G. Sumpter, Rajeev Kumar

Research output: Contribution to journal › Article › peer-review

10 Scopus citations

Abstract

We present a molecular dynamics simulation study investigating the phase behavior of lamellae-forming diblock copolymers with a single ionic junction on the backbone. Our results show qualitative agreement with experimental findings regarding enhanced microphase separation with the introduction of an ionic junction at the conjunction point, while further revealing nonmonotonic changes in domain spacing and order-disorder transition as a function of the electrostatic interaction strength. This highlights the dominant roles of entropic and binding effects of counterions under weak and strong ionic correlations, respectively. The location of the ionic junction is found to effectively modulate the charge distribution and chain conformation in the ordered domains; its presence in the middle of a block promotes folding of the block, leading to a smaller domain size. These findings demonstrate the interplay of ionic coupling with steric hindrance and chain end effects, which enhances our understanding of the delicate control over the microphase domain features.

Original language	English
Pages (from-to)	1667-1673
Number of pages	7
Journal	ACS Macro Letters
Volume	9
Issue number	11
DOIs	https://doi.org/10.1021/acsmacrolett.0c00592
State	Published - Nov 17 2020

Funding

This work was performed at Oak Ridge National Laboratory’s Center for Nanophase Materials Sciences, a U.S. Department of Energy Office of Science User Facility. This research used resources of the Compute and Data Environment for Science (CADES) and the Oak Ridge Leadership Computing Facility (OLCF), which are supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC05-00OR22725. This manuscript has been authored by UT-Battelle, LLC, under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The U.S. Government is authorized to reproduce and distribute reprints for government purposes notwithstanding any copyright notation hereon. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-publicaccess-plan ).

Funders	Funder number
CADES
Data Environment for Science
Oak Ridge National Laboratory
U.S. Department of Energy	DE-AC05-00OR22725
Office of Science

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abstract = "We present a molecular dynamics simulation study investigating the phase behavior of lamellae-forming diblock copolymers with a single ionic junction on the backbone. Our results show qualitative agreement with experimental findings regarding enhanced microphase separation with the introduction of an ionic junction at the conjunction point, while further revealing nonmonotonic changes in domain spacing and order-disorder transition as a function of the electrostatic interaction strength. This highlights the dominant roles of entropic and binding effects of counterions under weak and strong ionic correlations, respectively. The location of the ionic junction is found to effectively modulate the charge distribution and chain conformation in the ordered domains; its presence in the middle of a block promotes folding of the block, leading to a smaller domain size. These findings demonstrate the interplay of ionic coupling with steric hindrance and chain end effects, which enhances our understanding of the delicate control over the microphase domain features.",

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N1 - Publisher Copyright: ©

PY - 2020/11/17

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N2 - We present a molecular dynamics simulation study investigating the phase behavior of lamellae-forming diblock copolymers with a single ionic junction on the backbone. Our results show qualitative agreement with experimental findings regarding enhanced microphase separation with the introduction of an ionic junction at the conjunction point, while further revealing nonmonotonic changes in domain spacing and order-disorder transition as a function of the electrostatic interaction strength. This highlights the dominant roles of entropic and binding effects of counterions under weak and strong ionic correlations, respectively. The location of the ionic junction is found to effectively modulate the charge distribution and chain conformation in the ordered domains; its presence in the middle of a block promotes folding of the block, leading to a smaller domain size. These findings demonstrate the interplay of ionic coupling with steric hindrance and chain end effects, which enhances our understanding of the delicate control over the microphase domain features.

AB - We present a molecular dynamics simulation study investigating the phase behavior of lamellae-forming diblock copolymers with a single ionic junction on the backbone. Our results show qualitative agreement with experimental findings regarding enhanced microphase separation with the introduction of an ionic junction at the conjunction point, while further revealing nonmonotonic changes in domain spacing and order-disorder transition as a function of the electrostatic interaction strength. This highlights the dominant roles of entropic and binding effects of counterions under weak and strong ionic correlations, respectively. The location of the ionic junction is found to effectively modulate the charge distribution and chain conformation in the ordered domains; its presence in the middle of a block promotes folding of the block, leading to a smaller domain size. These findings demonstrate the interplay of ionic coupling with steric hindrance and chain end effects, which enhances our understanding of the delicate control over the microphase domain features.

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Modulating Microphase Separation of Lamellae-Forming Diblock Copolymers via Ionic Junctions

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