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Title: A Detailed Examination of the Topological Constraints of Lamellae-Forming Block Copolymers

Abstract

A microscopic molecular model of polymeric molecules that captures the effects of topological constraints is used to consider how microphase segregation can alter the distribution of entanglements both in space and along chain contours. Such topological constraints are obtained by using the Z1 algorithm, and it is found that for diblock copolymers in the lamellar morphology they are not homogeneously distributed, but instead exhibit a spatial dependence as a consequence of the self-organization of the polymer blocks. The specific shape of the inhomogeneous distribution is affected by the molecular weight of the copolymer. The microscopic information obtained by these calculations is then compared with the corresponding results generated from a coarser description of entangled block copolymers that includes soft intermolecular interactions and slip-springs, whose role is to incorporate the effects of entanglements that are lost during coarse-graining. Finally, this comparison is helpful for improving coarse-grained simulation approaches for use in multiscale studies of large-scale, self-assembled multicomponent polymer systems.

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [2]; ORCiD logo [4]; ORCiD logo [3]; ORCiD logo [5]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division & Inst. for Molecular Engineering; Univ. of Chicago, IL (United States). Inst. for Molecular Engineering
  2. Univ. of Chicago, IL (United States). Inst. for Molecular Engineering
  3. Georg-August Univ., Gottingen (Germany). Inst. fur Theoretische Physik
  4. Illinois Inst. of Technology, Chicago, IL (United States). Center for Molecular Study of Condensed Soft Matter, Dept. of Chemical and Biological Engineering and Dept. of Physics, Dept. of Applied Mathematics
  5. Federal Inst. of Technology, Zurich (Switzerland). Polymer Physics, Dept. of Materials
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; German Science Foundation; National Science Foundation (NSF); Swiss National Science Foundation (SNSF)
OSTI Identifier:
1459891
Grant/Contract Number:  
AC02-06CH11357; 1674/16-1; 200021_156106; CBET 1438700
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 51; Journal Issue: 5; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Ramirez-Hernandez, Abelardo, Peters, Brandon L., Schneider, Ludwig, Andreev, Marat, Schieber, Jay D., Muller, Marcus, Kroger, Martin, and de Pablo, Juan J. A Detailed Examination of the Topological Constraints of Lamellae-Forming Block Copolymers. United States: N. p., 2018. Web. doi:10.1021/acs.macromol.7b01485.
Ramirez-Hernandez, Abelardo, Peters, Brandon L., Schneider, Ludwig, Andreev, Marat, Schieber, Jay D., Muller, Marcus, Kroger, Martin, & de Pablo, Juan J. A Detailed Examination of the Topological Constraints of Lamellae-Forming Block Copolymers. United States. https://doi.org/10.1021/acs.macromol.7b01485
Ramirez-Hernandez, Abelardo, Peters, Brandon L., Schneider, Ludwig, Andreev, Marat, Schieber, Jay D., Muller, Marcus, Kroger, Martin, and de Pablo, Juan J. Mon . "A Detailed Examination of the Topological Constraints of Lamellae-Forming Block Copolymers". United States. https://doi.org/10.1021/acs.macromol.7b01485. https://www.osti.gov/servlets/purl/1459891.
@article{osti_1459891,
title = {A Detailed Examination of the Topological Constraints of Lamellae-Forming Block Copolymers},
author = {Ramirez-Hernandez, Abelardo and Peters, Brandon L. and Schneider, Ludwig and Andreev, Marat and Schieber, Jay D. and Muller, Marcus and Kroger, Martin and de Pablo, Juan J.},
abstractNote = {A microscopic molecular model of polymeric molecules that captures the effects of topological constraints is used to consider how microphase segregation can alter the distribution of entanglements both in space and along chain contours. Such topological constraints are obtained by using the Z1 algorithm, and it is found that for diblock copolymers in the lamellar morphology they are not homogeneously distributed, but instead exhibit a spatial dependence as a consequence of the self-organization of the polymer blocks. The specific shape of the inhomogeneous distribution is affected by the molecular weight of the copolymer. The microscopic information obtained by these calculations is then compared with the corresponding results generated from a coarser description of entangled block copolymers that includes soft intermolecular interactions and slip-springs, whose role is to incorporate the effects of entanglements that are lost during coarse-graining. Finally, this comparison is helpful for improving coarse-grained simulation approaches for use in multiscale studies of large-scale, self-assembled multicomponent polymer systems.},
doi = {10.1021/acs.macromol.7b01485},
journal = {Macromolecules},
number = 5,
volume = 51,
place = {United States},
year = {2018},
month = {3}
}

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Figures / Tables:

Figure 1 Figure 1: a) Schematic of the lamellae morphology, n is the unit vector perpendicular to the AB interface, and the coordinate z = 0 is located at the center of the A domain (blue). b) Definition of ∆s for the statistical segment length analysis. A value of ∆s = 4more » means there is a distance of 4 beads from the selected bead.« less

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