Topological Effects Near Order–Disorder Transitions in Symmetric Diblock Copolymer Melts
Abstract
The effects of polymer chain topology on the order–disorder transition of symmetric AB diblock copolymer melts are studied using coarse-grained molecular dynamics simulations. Specifically, we compared chain conformations near the lamellar-disordered transition in melts of symmetric (i.e., 50–50) AB diblock copolymers of linear chains, rings, and trefoil knots at the same chain lengths. The order (lamellar)–disorder transition temperature and the domain sizes both shifted to lower values with the introduction of topological constraints, leading to the following sequence: linear chains > rings > trefoil knots. Furthermore, investigation of the polymer chain conformations in terms of their radii of gyration, their writhe values (a measure for the degree of intertwining of a chain around itself), and their Jones polynomials (a method to measure entanglement of curves) showed that linear chains and rings remained stretched, while knots were stretched and tightened in disordered melts close to the lamellar-disorder transition. This work highlights chain topology as an important factor in affecting microphase separation in block copolymers.
- Authors:
-
[2];
[2];
[2]
- Univ. of Tennessee, Chattanooga, TN (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1814321
- Grant/Contract Number:
- AC05-00OR22725; DMS-1913180
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Macromolecules
- Additional Journal Information:
- Journal Volume: 54; Journal Issue: 16; Journal ID: ISSN 0024-9297
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; morphology; mathematical methods; homopolymers; polymers; copolymers
Citation Formats
Herschberg, Tom, Carrillo, Jan-Michael Y., Sumpter, Bobby G., Panagiotou, Eleni, and Kumar, Rajeev. Topological Effects Near Order–Disorder Transitions in Symmetric Diblock Copolymer Melts. United States: N. p., 2021.
Web. doi:10.1021/acs.macromol.1c00780.
Herschberg, Tom, Carrillo, Jan-Michael Y., Sumpter, Bobby G., Panagiotou, Eleni, & Kumar, Rajeev. Topological Effects Near Order–Disorder Transitions in Symmetric Diblock Copolymer Melts. United States. https://doi.org/10.1021/acs.macromol.1c00780
Herschberg, Tom, Carrillo, Jan-Michael Y., Sumpter, Bobby G., Panagiotou, Eleni, and Kumar, Rajeev. Wed .
"Topological Effects Near Order–Disorder Transitions in Symmetric Diblock Copolymer Melts". United States. https://doi.org/10.1021/acs.macromol.1c00780. https://www.osti.gov/servlets/purl/1814321.
@article{osti_1814321,
title = {Topological Effects Near Order–Disorder Transitions in Symmetric Diblock Copolymer Melts},
author = {Herschberg, Tom and Carrillo, Jan-Michael Y. and Sumpter, Bobby G. and Panagiotou, Eleni and Kumar, Rajeev},
abstractNote = {The effects of polymer chain topology on the order–disorder transition of symmetric AB diblock copolymer melts are studied using coarse-grained molecular dynamics simulations. Specifically, we compared chain conformations near the lamellar-disordered transition in melts of symmetric (i.e., 50–50) AB diblock copolymers of linear chains, rings, and trefoil knots at the same chain lengths. The order (lamellar)–disorder transition temperature and the domain sizes both shifted to lower values with the introduction of topological constraints, leading to the following sequence: linear chains > rings > trefoil knots. Furthermore, investigation of the polymer chain conformations in terms of their radii of gyration, their writhe values (a measure for the degree of intertwining of a chain around itself), and their Jones polynomials (a method to measure entanglement of curves) showed that linear chains and rings remained stretched, while knots were stretched and tightened in disordered melts close to the lamellar-disorder transition. This work highlights chain topology as an important factor in affecting microphase separation in block copolymers.},
doi = {10.1021/acs.macromol.1c00780},
journal = {Macromolecules},
number = 16,
volume = 54,
place = {United States},
year = {Wed Aug 11 00:00:00 EDT 2021},
month = {Wed Aug 11 00:00:00 EDT 2021}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Domain Spacing and Composition Profile Behavior in Salt-Doped Cyclic vs Linear Block Polymer Thin Films: A Joint Experimental and Simulation Study
journal, September 2017
- Gartner, Thomas E.; Kubo, Tomohiro; Seo, Youngmi
- Macromolecules, Vol. 50, Issue 18
Some statistical properties of flexible ring polymers
journal, February 1965
- Casassa, Edward F.
- Journal of Polymer Science Part A: General Papers, Vol. 3, Issue 2
Effects of Topological Constraints on Penetration Structures of Semi-Flexible Ring Polymers
journal, November 2020
- Guo, Fuchen; Li, Ke; Wu, Jiaxin
- Polymers, Vol. 12, Issue 11
Knot polynomials of open and closed curves
journal, August 2020
- Panagiotou, Eleni; Kauffman, Louis H.
- Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 476, Issue 2240
Theory of Microphase Separation in Block Copolymers
journal, November 1980
- Leibler, Ludwik
- Macromolecules, Vol. 13, Issue 6
Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995
- Plimpton, Steve
- Journal of Computational Physics, Vol. 117, Issue 1
Shape of unperturbed linear polymers: polypropylene
journal, November 1985
- Theodorou, Doros N.; Suter, Ulrich W.
- Macromolecules, Vol. 18, Issue 6
Microscopic Theory of Long-Time Center-of-Mass Self-Diffusion and Anomalous Transport in Ring Polymer Liquids
journal, November 2020
- Mei, Baicheng; Dell, Zachary E.; Schweizer, Kenneth S.
- Macromolecules, Vol. 53, Issue 23
A Trefoil Knotted Polymer Produced through Ring Expansion
journal, February 2015
- Cao, Peng-Fei; Mangadlao, Joey; Advincula, Rigoberto
- Angewandte Chemie, Vol. 127, Issue 17
Counting polymer knots to find the entanglement length
journal, January 2011
- Qin, Jian; Milner, Scott T.
- Soft Matter, Vol. 7, Issue 22
Lattice self-consistent field calculations of confined symmetric block copolymers of various chain architectures
journal, January 2020
- Zhang, Jingxue; Wu, Jiaping; Jiang, Run
- Soft Matter, Vol. 16, Issue 17
Flory-Huggins parameter χ, from binary mixtures of Lennard-Jones particles to block copolymer melts
journal, February 2014
- Chremos, Alexandros; Nikoubashman, Arash; Panagiotopoulos, Athanassios Z.
- The Journal of Chemical Physics, Vol. 140, Issue 5
Molecular-dynamics study of a three-dimensional one-component model for distortive phase transitions
journal, February 1978
- Schneider, T.; Stoll, E.
- Physical Review B, Vol. 17, Issue 3
Synthesizing a Trefoil Knotted Block Copolymer via Ring-Expansion Strategy
journal, February 2017
- Cao, Peng-Fei; Rong, Li-Han; Mangadlao, Joey Dacula
- Macromolecules, Vol. 50, Issue 4
Microphase separation of block copolymer rings
journal, March 1993
- Marko, J. F.
- Macromolecules, Vol. 26, Issue 6
Dynamics of supercoiled DNA with complex knots: large-scale rearrangements and persistent multi-strand interlocking
journal, June 2018
- Coronel, Lucia; Suma, Antonio; Micheletti, Cristian
- Nucleic Acids Research, Vol. 46, Issue 15
Threading–Unthreading Transition of Linear-Ring Polymer Blends in Extensional Flow
journal, October 2020
- Borger, Anine; Wang, Wendi; O’Connor, Thomas C.
- ACS Macro Letters, Vol. 9, Issue 10
Block Copolymer Theory. 4. Narrow Interphase Approximation
journal, November 1976
- Helfand, Eugene; Wasserman, Z. R.
- Macromolecules, Vol. 9, Issue 6
Cyclic Block Copolymers for Controlling Feature Sizes in Block Copolymer Lithography
journal, November 2012
- Poelma, Justin E.; Ono, Kosuke; Miyajima, Daigo
- ACS Nano, Vol. 6, Issue 12
Trefoil Knot Hydrodynamic Delocalization on Sheared Ring Polymers
journal, March 2018
- Liebetreu, Maximilian; Ripoll, Marisol; Likos, Christos N.
- ACS Macro Letters, Vol. 7, Issue 4
The Writhing Number of a Space Curve
journal, April 1971
- Fuller, F. B.
- Proceedings of the National Academy of Sciences, Vol. 68, Issue 4
Conservation of complex knotting and slipknotting patterns in proteins
journal, June 2012
- Sulkowska, J. I.; Rawdon, E. J.; Millett, K. C.
- Proceedings of the National Academy of Sciences, Vol. 109, Issue 26
Influence of knot complexity on glass-formation in low molecular mass ring polymer melts
journal, March 2019
- Vargas-Lara, Fernando; Pazmiño Betancourt, Beatriz A.; Douglas, Jack F.
- The Journal of Chemical Physics, Vol. 150, Issue 10
Block Copolymer Thermodynamics: Theory and Experiment
journal, October 1990
- Bates, Frank S.; Fredrickson, Glenn H.
- Annual Review of Physical Chemistry, Vol. 41, Issue 1
Hecke Algebra Representations of Braid Groups and Link Polynomials
journal, September 1987
- Jones, V. F. R.
- The Annals of Mathematics, Vol. 126, Issue 2
Intrinsic Surface Characteristics and Dynamic Mechanisms of Ring Polymers in Solution and Melt under Shear Flow
journal, November 2020
- Jeong, Seung Heum; Cho, Soowon; Roh, Eun Jung
- Macromolecules, Vol. 53, Issue 22
Self-Consistent Field Theory of Gaussian Ring Polymers
journal, March 2012
- Kim, Jaeup U.; Yang, Yong-Biao; Lee, Won Bo
- Macromolecules, Vol. 45, Issue 7
Statistical mechanics of supercoils and the torsional stiffness of the DNA double helix
journal, July 1979
- Vologodskii, A. V.; Anshelevich, V. V.; Lukashin, A. V.
- Nature, Vol. 280, Issue 5720
Dynamics of entangled linear polymer melts: A molecular‐dynamics simulation
journal, April 1990
- Kremer, Kurt; Grest, Gary S.
- The Journal of Chemical Physics, Vol. 92, Issue 8
Effect of Knotting on the Shape of Polymers
journal, November 2008
- Rawdon, Eric J.; Kern, John C.; Piatek, Michael
- Macromolecules, Vol. 41, Issue 21
Multicyclic Polymer Synthesis through Controlled/Living Cyclopolymerization of α,ω-Dinorbornenyl-Functionalized Macromonomers
journal, May 2018
- Isono, Takuya; Sasamori, Tetsuya; Honda, Kohei
- Macromolecules, Vol. 51, Issue 10
Implementing molecular dynamics on hybrid high performance computers – short range forces
journal, April 2011
- Brown, W. Michael; Wang, Peng; Plimpton, Steven J.
- Computer Physics Communications, Vol. 182, Issue 4
Bicyclic Topology Transforms Self-Assembled Nanostructures in Block Copolymer Thin Films
journal, July 2020
- Ree, Brian J.; Satoh, Yusuke; Isono, Takuya
- Nano Letters, Vol. 20, Issue 9
Discovering privileged topologies of molecular knots with self-assembling models
journal, August 2018
- Marenda, Mattia; Orlandini, Enzo; Micheletti, Cristian
- Nature Communications, Vol. 9, Issue 1
Synthesis of Well-Defined Three- and Four-Armed Cage-Shaped Polymers via “Topological Conversion” from Trefoil- and Quatrefoil-Shaped Polymers
journal, December 2016
- Satoh, Yusuke; Matsuno, Hirohiko; Yamamoto, Takuya
- Macromolecules, Vol. 50, Issue 1
Molecular dynamics with coupling to an external bath
journal, October 1984
- Berendsen, H. J. C.; Postma, J. P. M.; van Gunsteren, W. F.
- The Journal of Chemical Physics, Vol. 81, Issue 8
Intricate Knots in Proteins: Function and Evolution
journal, September 2006
- Virnau, Peter; Mirny, Leonid A.; Kardar, Mehran
- PLoS Computational Biology, Vol. 2, Issue 9
Statistics of Knots, Geometry of Conformations, and Evolution of Proteins
journal, May 2006
- Lua, Rhonald C.; Grosberg, Alexander Y.
- PLoS Computational Biology, Vol. 2, Issue 5
Knot Energy, Complexity, and Mobility of Knotted Polymers
journal, October 2017
- Vargas–Lara, Fernando; Hassan, Ahmed M.; Mansfield, Marc L.
- Scientific Reports, Vol. 7, Issue 1
Understanding the effects of dipolar interactions on the thermodynamics of diblock copolymer melts
journal, August 2019
- Kumar, Rajeev; Li, Wei; Sumpter, Bobby G.
- The Journal of Chemical Physics, Vol. 151, Issue 5
Recent progress on the synthesis of cyclic polymers via ring-expansion strategies
journal, May 2017
- Chang, Young A.; Waymouth, Robert M.
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 55, Issue 18
On Types of Knotted Curves
journal, January 1926
- Alexander, J. W.; Briggs, G. B.
- The Annals of Mathematics, Vol. 28, Issue 1/4
Polyelectrolytes in Salt Solutions: Molecular Dynamics Simulations
journal, July 2011
- Carrillo, Jan-Michael Y.; Dobrynin, Andrey V.
- Macromolecules, Vol. 44, Issue 14
Hydrodynamics and Filtering of Knotted Ring Polymers in Nanochannels
journal, May 2019
- Weiss, Lisa B.; Marenda, Mattia; Micheletti, Cristian
- Macromolecules, Vol. 52, Issue 11
Topological rigidification of flexible polymers in solution
conference, January 2018
- Douglas, Jack F.; Vargas–Lara, Fernando
- 9TH INTERNATIONAL CONFERENCE ON “TIMES OF POLYMERS AND COMPOSITES”: From Aerospace to Nanotechnology, AIP Conference Proceedings
Topological Methods for Polymeric Materials: Characterizing the Relationship Between Polymer Entanglement and Viscoelasticity
journal, March 2019
- Panagiotou, Eleni; Millett, Kenneth; Atzberger, Paul
- Polymers, Vol. 11, Issue 3
Conformation and dynamics of ring polymers under symmetric thin film confinement
journal, November 2020
- Zhang, Tianren; Winey, Karen I.; Riggleman, Robert A.
- The Journal of Chemical Physics, Vol. 153, Issue 18
Viscosity of Ring Polymer Melts
journal, September 2013
- Pasquino, Rossana; Vasilakopoulos, Thodoris C.; Jeong, Youn Cheol
- ACS Macro Letters, Vol. 2, Issue 10
Modulating Microphase Separation of Lamellae-Forming Diblock Copolymers via Ionic Junctions
journal, October 2020
- Li, Wei; Carrillo, Jan-Michael Y.; Sumpter, Bobby G.
- ACS Macro Letters, Vol. 9, Issue 11
Impact of Cyclic Block Copolymer Chain Architecture and Degree of Polymerization on Nanoscale Domain Spacing: A Simulation and Scaling Theory Analysis
journal, November 2019
- Goodson, Amy D.; Troxler, Jessie E.; Rick, Maxwell S.
- Macromolecules, Vol. 52, Issue 23