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Title: Understanding the effects of dipolar interactions on the thermodynamics of diblock copolymer melts

Abstract

We present results highlighting the roles of dipolar interactions in affecting thermodynamics of diblock copolymer melts. Field theoretic methods and coarse-grained molecular dynamics (MD) simulations are used to understand the effects of dipolar interactions among copolymer segments. In particular, the effects of dipolar interactions on disorder-lamellar transition and domain spacing of the lamellar morphology are studied. It is shown that dipolar interactions stabilize the lamellar morphology over the disordered phase. Furthermore, the domain spacing for the lamellar morphology is predicted to increase with an increase in disparity between dipole moments of two kinds of monomers in the diblock or equivalently a mismatch in the dielectric constant of homopolymers forming the diblock. MD simulations reveal that additional orientational effects resulting from the anisotropic nature of the dipolar interaction potential are significant for highly polar monomers. In contrast, the field theoretic models based on orientationally averaged dipolar interaction potentials, such as those used in this work, fail to capture the effects of orientational correlations.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]
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  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Univ. of Massachusetts, Amherst, MA (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1546508
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 5; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Kumar, Rajeev, Li, Wei, Sumpter, Bobby G., and Muthukumar, Murugappan. Understanding the effects of dipolar interactions on the thermodynamics of diblock copolymer melts. United States: N. p., 2019. Web. doi:10.1063/1.5114799.
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Kumar, Rajeev, Li, Wei, Sumpter, Bobby G., & Muthukumar, Murugappan. Understanding the effects of dipolar interactions on the thermodynamics of diblock copolymer melts. United States. https://doi.org/10.1063/1.5114799
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Kumar, Rajeev, Li, Wei, Sumpter, Bobby G., and Muthukumar, Murugappan. Thu . "Understanding the effects of dipolar interactions on the thermodynamics of diblock copolymer melts". United States. https://doi.org/10.1063/1.5114799. https://www.osti.gov/servlets/purl/1546508.
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@article{osti_1546508,
title = {Understanding the effects of dipolar interactions on the thermodynamics of diblock copolymer melts},
author = {Kumar, Rajeev and Li, Wei and Sumpter, Bobby G. and Muthukumar, Murugappan},
abstractNote = {We present results highlighting the roles of dipolar interactions in affecting thermodynamics of diblock copolymer melts. Field theoretic methods and coarse-grained molecular dynamics (MD) simulations are used to understand the effects of dipolar interactions among copolymer segments. In particular, the effects of dipolar interactions on disorder-lamellar transition and domain spacing of the lamellar morphology are studied. It is shown that dipolar interactions stabilize the lamellar morphology over the disordered phase. Furthermore, the domain spacing for the lamellar morphology is predicted to increase with an increase in disparity between dipole moments of two kinds of monomers in the diblock or equivalently a mismatch in the dielectric constant of homopolymers forming the diblock. MD simulations reveal that additional orientational effects resulting from the anisotropic nature of the dipolar interaction potential are significant for highly polar monomers. In contrast, the field theoretic models based on orientationally averaged dipolar interaction potentials, such as those used in this work, fail to capture the effects of orientational correlations.},
doi = {10.1063/1.5114799},
journal = {Journal of Chemical Physics},
number = 5,
volume = 151,
place = {United States},
year = {Thu Aug 01 00:00:00 EDT 2019},
month = {Thu Aug 01 00:00:00 EDT 2019}
}
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https://doi.org/10.1063/1.5114799
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Cited by: 13 works
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Figures / Tables:

FIG. 1 FIG. 1: Characteristics of the stability limit for the disordered phase as a function of the mismatch between the monomeric dipole moments in the diblock copolymer melts. (a) Length scale of the ordered morphology to appear as a function of p4. (b) Stability limit of the disordered phase without consideringmore » renormalization of χAB due to the dipolar interactions. (c) Stability limit of the disordered phase after considering renormalization of χAB [cf. Eq. (6)]. N = 1000 and f A = 0.5 are used for the calculations.« less
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