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

Title: On the order-disorder transition of compressible diblock copolymer melts

Abstract

We performed both the fast off-lattice Monte Carlo simulations of symmetric diblock copolymers (DBC) in an isothermal-isobaric ensemble and the self-consistent field calculations of asymmetric DBC to properly determine the order-disorder transition (ODT) of a model system of compressible DBC melts used in the literature when it is a first-order phase transition, and studied for the first time the co-existence of the two phases at ODT. We found that the co-existing region is quite small and decreases as the system becomes less compressible, which justifies the previous ODT results obtained by equating the Helmholtz free energy per chain of the two phases. We also found that for the most compressible system where there is no repulsion between the same type of segments, the self-consistent field theory predicts that ODT is a second-order phase transition even for asymmetric DBC melts due to its mean-field approximation.

Authors:
 [1];  [1]
  1. Colorado State Univ., Fort Collins, CO (United States)
Publication Date:
Research Org.:
Colorado State Univ., Fort Collins, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1469644
Alternate Identifier(s):
OSTI ID: 1225768
Grant/Contract Number:  
FG02-07ER46448
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 143; Journal Issue: 18; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Zong, Jing, and Wang, Qiang. On the order-disorder transition of compressible diblock copolymer melts. United States: N. p., 2015. Web. doi:10.1063/1.4934992.
Zong, Jing, & Wang, Qiang. On the order-disorder transition of compressible diblock copolymer melts. United States. doi:https://doi.org/10.1063/1.4934992
Zong, Jing, and Wang, Qiang. Wed . "On the order-disorder transition of compressible diblock copolymer melts". United States. doi:https://doi.org/10.1063/1.4934992. https://www.osti.gov/servlets/purl/1469644.
@article{osti_1469644,
title = {On the order-disorder transition of compressible diblock copolymer melts},
author = {Zong, Jing and Wang, Qiang},
abstractNote = {We performed both the fast off-lattice Monte Carlo simulations of symmetric diblock copolymers (DBC) in an isothermal-isobaric ensemble and the self-consistent field calculations of asymmetric DBC to properly determine the order-disorder transition (ODT) of a model system of compressible DBC melts used in the literature when it is a first-order phase transition, and studied for the first time the co-existence of the two phases at ODT. We found that the co-existing region is quite small and decreases as the system becomes less compressible, which justifies the previous ODT results obtained by equating the Helmholtz free energy per chain of the two phases. We also found that for the most compressible system where there is no repulsion between the same type of segments, the self-consistent field theory predicts that ODT is a second-order phase transition even for asymmetric DBC melts due to its mean-field approximation.},
doi = {10.1063/1.4934992},
journal = {Journal of Chemical Physics},
number = 18,
volume = 143,
place = {United States},
year = {2015},
month = {11}
}

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:

Simulating Microscopic Hydrodynamic Phenomena with Dissipative Particle Dynamics
journal, June 1992


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

Universality of Block Copolymer Melts
journal, August 2014


Phase transitions in diblock copolymers: Theory and Monte Carlo simulations
journal, July 1993


Fast off-lattice Monte Carlo simulations of soft-core spherocylinders: Isotropic-nematic transition and comparisons with virial expansion
journal, October 2012

  • Zong, Jing; Zhang, Xinghua; Wang, Qiang
  • The Journal of Chemical Physics, Vol. 137, Issue 13
  • DOI: 10.1063/1.4755959

Concentration fluctuation effects on the phase behavior of compressible diblock copolymers
journal, May 2004

  • Cho, Junhan
  • The Journal of Chemical Physics, Vol. 120, Issue 20
  • DOI: 10.1063/1.1724819

Replica-exchange Monte Carlo method for the isobaric–isothermal ensemble
journal, March 2001


Theory of Microphase Separation in Block Copolymers
journal, November 1980


Lattice cluster theory of compressible diblock copolymer melts
journal, March 1994

  • Dudowicz, Jacek; Freed, Karl F.
  • The Journal of Chemical Physics, Vol. 100, Issue 6
  • DOI: 10.1063/1.466248

High-Pressure Effects on the Order−Disorder Transition in Block Copolymer Melts
journal, January 1996

  • Hajduk, Damian A.; Gruner, Sol M.; Erramilli, Shyamsunder
  • Macromolecules, Vol. 29, Issue 5
  • DOI: 10.1021/ma950643c

On the comparisons between dissipative particle dynamics simulations and self-consistent field calculations of diblock copolymer microphase separation
journal, May 2013

  • Sandhu, Paramvir; Zong, Jing; Yang, Delian
  • The Journal of Chemical Physics, Vol. 138, Issue 19
  • DOI: 10.1063/1.4804608

Theoretically informed coarse grain simulations of polymeric systems
journal, August 2009

  • Pike, Darin Q.; Detcheverry, François A.; Müller, Marcus
  • The Journal of Chemical Physics, Vol. 131, Issue 8
  • DOI: 10.1063/1.3187936

Theory of the Interface between Immiscible Polymers. II
journal, April 1972

  • Helfand, Eugene; Tagami, Yukiko
  • The Journal of Chemical Physics, Vol. 56, Issue 7
  • DOI: 10.1063/1.1677735

Fluctuation/correlation effects in symmetric diblock copolymers: On the order-disorder transition
journal, September 2013

  • Zong, Jing; Wang, Qiang
  • The Journal of Chemical Physics, Vol. 139, Issue 12
  • DOI: 10.1063/1.4821815

The microphase separation transition in symmetric diblock copolymer melts: A Monte Carlo study
journal, June 1991

  • Fried, H.; Binder, K.
  • The Journal of Chemical Physics, Vol. 94, Issue 12
  • DOI: 10.1063/1.460067

Calculating the free energy of self-assembled structures by thermodynamic integration
journal, January 2008

  • Müller, Marcus; Daoulas, Kostas Ch.
  • The Journal of Chemical Physics, Vol. 128, Issue 2
  • DOI: 10.1063/1.2818565

Quantitative Study of Fluctuation Effects by Fast Lattice Monte Carlo Simulations. V. Incompressible Homopolymer Melts
journal, October 2014

  • Zhang, Pengfei; Yang, Delian; Wang, Qiang
  • The Journal of Physical Chemistry B, Vol. 118, Issue 41
  • DOI: 10.1021/jp507391j

Computer Simulation of Static and Dynamic Behavior of Diblock Copolymer Melts
journal, December 1997

  • Pakula, T.; Karatasos, K.; Anastasiadis, S. H.
  • Macromolecules, Vol. 30, Issue 26
  • DOI: 10.1021/ma9605107

Monte Carlo phase diagram for diblock copolymer melts
journal, January 2006

  • Matsen, M. W.; Griffiths, G. H.; Wickham, R. A.
  • The Journal of Chemical Physics, Vol. 124, Issue 2
  • DOI: 10.1063/1.2140286

Monte Carlo simulation of phase separations of block copolymers and of corresponding blends
journal, July 1994


Lower critical ordering temperature in diblock copolymer melts
journal, March 1994


Simulation of Lamellar Phase Transitions in Block Copolymers and Surfactants
journal, October 1994


Monte Carlo Simulation of Coarse Grain Polymeric Systems
journal, May 2009


Orthorhombic F d d d Network in Triblock and Diblock Copolymer Melts
journal, May 2005


Free Energy Evaluation in Field-Theoretic Polymer Simulations
journal, September 2008


Long-range density fluctuations in a symmetric diblock copolymer
journal, October 1999


Phase coexistence and critical point determination in polydisperse fluids
journal, February 2001


Effects of interaction range and compressibility on the microphase separation of diblock copolymers: Mean-field analysis
journal, August 2008

  • Wang, Qiang
  • The Journal of Chemical Physics, Vol. 129, Issue 5
  • DOI: 10.1063/1.2962978

On the large entropic contribution to the effective interaction parameter of polystyrene–poly(methyl methacrylate) diblock copolymer systems
journal, August 1992

  • Freed, Karl F.; Dudowicz, Jacek
  • The Journal of Chemical Physics, Vol. 97, Issue 3
  • DOI: 10.1063/1.463149

Monte Carlo Field-Theoretic Simulations for Melts of Symmetric Diblock Copolymer
journal, September 2013

  • Stasiak, P.; Matsen, M. W.
  • Macromolecules, Vol. 46, Issue 19
  • DOI: 10.1021/ma401687j

Optimized Monte Carlo data analysis
journal, September 1989


Density Discontinuity at the Microphase Separation Transition of a Symmetric Diblock Copolymer
journal, June 1995


Dynamic simulation of diblock copolymer microphase separation
journal, May 1998

  • Groot, Robert D.; Madden, Timothy J.
  • The Journal of Chemical Physics, Vol. 108, Issue 20
  • DOI: 10.1063/1.476300

Monte Carlo phase diagram for diblock copolymer melts
journal, July 2010


Analysis of Phase Separation in Compressible Polymer Blends and Block Copolymers
journal, March 2000


Fluctuation effects in block copolymer melts
journal, January 2003

  • Vassiliev, O. N.; Matsen, M. W.
  • The Journal of Chemical Physics, Vol. 118, Issue 16
  • DOI: 10.1063/1.1562616

Theory of the interface between immiscible polymers
journal, October 1971

  • Helfand, Eugene; Tagami, Yukiko
  • Journal of Polymer Science Part B: Polymer Letters, Vol. 9, Issue 10
  • DOI: 10.1002/pol.1971.110091006

Fast off-lattice Monte Carlo simulations with “soft” repulsive potentials
journal, March 2009

  • Wang, Qiang; Yin, Yuhua
  • The Journal of Chemical Physics, Vol. 130, Issue 10
  • DOI: 10.1063/1.3086606

Molecular Simulation of Sucrose Solutions near the Glass Transition Temperature
journal, February 2001

  • Ekdawi-Sever, Nancy C.; Conrad, Paul B.; de Pablo, Juan J.
  • The Journal of Physical Chemistry A, Vol. 105, Issue 4
  • DOI: 10.1021/jp002722i

Interface Orientation and Chain Conformation in Simulated Symmetric Diblock Copolymer Lamellar Systems
journal, January 2005

  • Yang, Jian; Winnik, Mitchell A.; Pakula, Tadeusz
  • Macromolecular Theory and Simulations, Vol. 14, Issue 1
  • DOI: 10.1002/mats.200400073

Computer simulation of copolymer phase behavior
journal, December 2002

  • Schultz, Andrew J.; Hall, Carol K.; Genzer, Jan
  • The Journal of Chemical Physics, Vol. 117, Issue 22
  • DOI: 10.1063/1.1519839

Analysis of Compressible Diblock Copolymer Melts That Microphase Separate upon Cooling
journal, August 2001


Concentration and energy fluctuations in a critical polymer mixture
journal, March 1995


Simulation of Lamellar Phase Transitions in Block Copolymers
journal, July 1994


Enthalpic and Volumetric Changes at Phase Transitions of Polystyrene- b -poly(alkyl methacrylate) Copolymers and Their Pressure Dependence
journal, March 2014

  • Lee, Dong Hyun; Lee, Hoyeon; Lee, Yonghoon
  • Macromolecules, Vol. 47, Issue 6
  • DOI: 10.1021/ma402535w

Statics and dynamics of dense copolymer melts: A Monte Carlo simulation study
journal, April 1997

  • Hoffmann, Alexander; Sommer, Jens-Uwe; Blumen, Alexander
  • The Journal of Chemical Physics, Vol. 106, Issue 16
  • DOI: 10.1063/1.473668

Efficient continuum model for simulating polymer blends and copolymers
journal, December 1996

  • Grest, Gary S.; Lacasse, Martin‐D.; Kremer, Kurt
  • The Journal of Chemical Physics, Vol. 105, Issue 23
  • DOI: 10.1063/1.472978

The diagonal bond method: A new lattice polymer model for simulation study of block copolymers
journal, November 1996

  • Dotera, Tomonari; Hatano, Akira
  • The Journal of Chemical Physics, Vol. 105, Issue 18
  • DOI: 10.1063/1.472696

Use of the Weighted Histogram Analysis Method for the Analysis of Simulated and Parallel Tempering Simulations
journal, November 2006

  • Chodera, John D.; Swope, William C.; Pitera, Jed W.
  • Journal of Chemical Theory and Computation, Vol. 3, Issue 1
  • DOI: 10.1021/ct0502864

Universal Phenomenology of Symmetric Diblock Copolymers near the Order–Disorder Transition
journal, January 2015

  • Medapuram, Pavani; Glaser, Jens; Morse, David C.
  • Macromolecules, Vol. 48, Issue 3
  • DOI: 10.1021/ma5017264

Computer simulations of asymmetric block copolymers
journal, November 1997

  • Hoffmann, Alexander; Sommer, Jens-Uwe; Blumen, Alexander
  • The Journal of Chemical Physics, Vol. 107, Issue 18
  • DOI: 10.1063/1.474994

Statics and Dynamics of Symmetric Diblock Copolymers:  A Molecular Dynamics Study
journal, February 1999

  • Murat, Michael; Grest, Gary S.; Kremer, Kurt
  • Macromolecules, Vol. 32, Issue 3
  • DOI: 10.1021/ma981512p

Stable and unstable phases of a diblock copolymer melt
journal, April 1994