skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Intradomain phase transitions in flexible block copolymers with self-aligning segments

Abstract

We study a model of flexible block copolymers (BCPs) in which there is an enlthalpic preference for orientational order, or local alignment, among like-block segments. We describe a generalization of the self-consistent field theory of flexible BCPs to include inter-segment orientational interactions via a Landau-de Gennes free energy associated with a polar or nematic order parameter for segments of one component of a diblock copolymer. We study the equilibrium states of this model numerically, using a pseudo-spectral approach to solve for chain conformation statistics in the presence of a self-consistent torque generated by inter-segment alignment forces. Applying this theory to the structure of lamellar domains composed of symmetric diblocks possessing a single block of “self-aligning” polar segments, we show the emergence of spatially complex segment order parameters (segment director fields) within a given lamellar domain. Because BCP phase separation gives rise to spatially inhomogeneous orientation order of segments even in the absence of explicit intra-segment aligning forces, the director fields of BCPs, as well as thermodynamics of lamellar domain formation, exhibit a highly non-linear dependence on both the inter-block segregation ( χ N) and the enthalpy of alignment (ε). Specifically, we predict the stability of new phases of lamellar ordermore » in which distinct regions of alignment coexist within the single mesodomain and spontaneously break the symmetries of the lamella (or smectic) pattern of composition in the melt via in-plane tilt of the director in the centers of the like-composition domains. We further show that, in analogy to Freedericksz transition confined nematics, the elastic costs to reorient segments within the domain, as described by the Frank elasticity of the director, increase the threshold value ε needed to induce this intra-domain phase transition.« less

Authors:
ORCiD logo [1];  [1]
  1. Univ. of Massachusetts, Amherst, MA (United States)
Publication Date:
Research Org.:
Univ. of Massachusetts, Amherst, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1511689
Grant/Contract Number:  
SC0014549
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 148; Journal Issue: 17; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Burke, Christopher J., and Grason, Gregory M. Intradomain phase transitions in flexible block copolymers with self-aligning segments. United States: N. p., 2018. Web. doi:10.1063/1.5025809.
Burke, Christopher J., & Grason, Gregory M. Intradomain phase transitions in flexible block copolymers with self-aligning segments. United States. doi:10.1063/1.5025809.
Burke, Christopher J., and Grason, Gregory M. Fri . "Intradomain phase transitions in flexible block copolymers with self-aligning segments". United States. doi:10.1063/1.5025809. https://www.osti.gov/servlets/purl/1511689.
@article{osti_1511689,
title = {Intradomain phase transitions in flexible block copolymers with self-aligning segments},
author = {Burke, Christopher J. and Grason, Gregory M.},
abstractNote = {We study a model of flexible block copolymers (BCPs) in which there is an enlthalpic preference for orientational order, or local alignment, among like-block segments. We describe a generalization of the self-consistent field theory of flexible BCPs to include inter-segment orientational interactions via a Landau-de Gennes free energy associated with a polar or nematic order parameter for segments of one component of a diblock copolymer. We study the equilibrium states of this model numerically, using a pseudo-spectral approach to solve for chain conformation statistics in the presence of a self-consistent torque generated by inter-segment alignment forces. Applying this theory to the structure of lamellar domains composed of symmetric diblocks possessing a single block of “self-aligning” polar segments, we show the emergence of spatially complex segment order parameters (segment director fields) within a given lamellar domain. Because BCP phase separation gives rise to spatially inhomogeneous orientation order of segments even in the absence of explicit intra-segment aligning forces, the director fields of BCPs, as well as thermodynamics of lamellar domain formation, exhibit a highly non-linear dependence on both the inter-block segregation (χN) and the enthalpy of alignment (ε). Specifically, we predict the stability of new phases of lamellar order in which distinct regions of alignment coexist within the single mesodomain and spontaneously break the symmetries of the lamella (or smectic) pattern of composition in the melt via in-plane tilt of the director in the centers of the like-composition domains. We further show that, in analogy to Freedericksz transition confined nematics, the elastic costs to reorient segments within the domain, as described by the Frank elasticity of the director, increase the threshold value ε needed to induce this intra-domain phase transition.},
doi = {10.1063/1.5025809},
journal = {Journal of Chemical Physics},
number = 17,
volume = 148,
place = {United States},
year = {2018},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Effect of Architecture on the Phase Behavior of AB-Type Block Copolymer Melts
journal, February 2012


Influence of elastic anisotropy on the structure of Neel inversion walls in liquid crystal polymers
journal, November 1993


Chirality Transfer in Block Copolymer Melts: Emerging Concepts
journal, April 2015


Fluctuation effects in the theory of microphase separation in block copolymers
journal, July 1987

  • Fredrickson, Glenn H.; Helfand, Eugene
  • The Journal of Chemical Physics, Vol. 87, Issue 1
  • DOI: 10.1063/1.453566

Intradomain Textures in Block Copolymers: Multizone Alignment and Biaxiality
journal, June 2017


Phase Behavior of Semiflexible Diblock Copolymers
journal, May 1994

  • Singh, Chandralekha; Goulian, Mark; Liu, Andrea J.
  • Macromolecules, Vol. 27, Issue 11
  • DOI: 10.1021/ma00089a013

Tensorial conservation law for nematic polymers
journal, November 2013


Self-assembly of rod–coil block copolymers
journal, March 2004

  • Pryamitsyn, Victor; Ganesan, Venkat
  • The Journal of Chemical Physics, Vol. 120, Issue 12
  • DOI: 10.1063/1.1649729

Polyisoprene-Polystyrene Diblock Copolymer Phase Diagram near the Order-Disorder Transition
journal, December 1995

  • Khandpur, Ashish K.; Foerster, Stephan; Bates, Frank S.
  • Macromolecules, Vol. 28, Issue 26
  • DOI: 10.1021/ma00130a012

A density functional theory of chiral block copolymer melts
journal, May 2013

  • Wang, Shih-Hao; Kawakatsu, Toshihiro; Chen, Peilong
  • The Journal of Chemical Physics, Vol. 138, Issue 19
  • DOI: 10.1063/1.4802963

Maier-Saupe model of polymer nematics: Comparing free energies calculated with Self Consistent Field theory and Monte Carlo simulations
journal, November 2016

  • Greco, Cristina; Jiang, Ying; Chen, Jeff Z. Y.
  • The Journal of Chemical Physics, Vol. 145, Issue 18
  • DOI: 10.1063/1.4966919

Theory of Microphase Separation in Block Copolymers
journal, November 1980


Complex liquid-crystal nanostructures in semiflexible ABC linear triblock copolymers: A self-consistent field theory
journal, November 2016

  • Li, Shiben; Jiang, Ying; Chen, Jeff Z. Y.
  • The Journal of Chemical Physics, Vol. 145, Issue 18
  • DOI: 10.1063/1.4967423

Polydispersity effects on the microphase-separation transition in block copolymers
journal, June 1990

  • Burger, C.; Ruland, W.; Semenov, A. N.
  • Macromolecules, Vol. 23, Issue 13
  • DOI: 10.1021/ma00215a021

Liquid-crystalline behavior of rod-coil diblock copolymers
journal, September 1998

  • Matsen, M. W.; Barrett, C.
  • The Journal of Chemical Physics, Vol. 109, Issue 10
  • DOI: 10.1063/1.477011

Orientational interactions in block copolymer melts: Self-consistent field theory
journal, September 2012

  • Zhao, Wei; Russell, Thomas P.; Grason, Gregory M.
  • The Journal of Chemical Physics, Vol. 137, Issue 10
  • DOI: 10.1063/1.4752198

Perspective: parameters in a self-consistent field theory of multicomponent wormlike-copolymer melts
journal, October 2016


Liquid-Crystalline Phases of Semiflexible Diblock Copolymer Melts
journal, July 1996


Transfer of Chirality from Molecule to Phase in Self-Assembled Chiral Block Copolymers
journal, June 2012

  • Ho, Rong-Ming; Li, Ming-Chia; Lin, Shih-Chieh
  • Journal of the American Chemical Society, Vol. 134, Issue 26
  • DOI: 10.1021/ja303513f

Broadly Accessible Self-Consistent Field Theory for Block Polymer Materials Discovery
journal, June 2016


Theory of inhomogeneous polymers: Fundamentals of the Gaussian random‐walk model
journal, February 1975

  • Helfand, Eugene
  • The Journal of Chemical Physics, Vol. 62, Issue 3
  • DOI: 10.1063/1.430517

Theory of wormlike polymer chains in confinement
journal, March 2016


Polymeric liquid crystals: Frank elasticity and light scattering
journal, August 1976


Block Copolymer Thermodynamics: Theory and Experiment
journal, October 1990


Chain Architecture and Asymmetry in Copolymer Microphases
journal, April 1994


Dependence of the disorder-lamellar stability boundary of a melt of asymmetric wormlike A B diblock copolymers on the chain rigidity
journal, October 2011


Improved numerical algorithm for exploring block copolymer mesophases
journal, July 2002

  • Rasmussen, K. �.; Kalosakas, G.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 40, Issue 16
  • DOI: 10.1002/polb.10238

The standard Gaussian model for block copolymer melts
journal, December 2001


Structure and tension of the interface between dilute polymer solutions
journal, June 1989

  • Szleifer, I.; Widom, B.
  • The Journal of Chemical Physics, Vol. 90, Issue 12
  • DOI: 10.1063/1.456186

Melts of semiflexible diblock copolymer
journal, May 1996

  • Matsen, M. W.
  • The Journal of Chemical Physics, Vol. 104, Issue 19
  • DOI: 10.1063/1.471481

Density-conformation coupling in macromolecular systems: polymer interfaces
journal, January 1990