Modulating Microphase Separation of Lamellae-Forming Diblock Copolymers via Ionic Junctions
Abstract
In this work, we present a molecular dynamics simulation study investigating the phase behavior of lamellae-forming diblock copolymers with a single ionic junction on the backbone. Our results show qualitative agreement with experimental findings regarding enhanced microphase separation with the introduction of an ionic junction at the conjunction point, while further revealing nonmonotonic changes in domain spacing and order–disorder transition as a function of the electrostatic interaction strength. This highlights the dominant roles of entropic and binding effects of counterions under weak and strong ionic correlations, respectively. The location of the ionic junction is found to effectively modulate the charge distribution and chain conformation in the ordered domains; its presence in the middle of a block promotes folding of the block, leading to a smaller domain size. These findings demonstrate the interplay of ionic coupling with steric hindrance and chain end effects, which enhances our understanding of the delicate control over the microphase domain features.
- Authors:
-
[1];
[2];
[2];
[2]
- Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- 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)
- OSTI Identifier:
- 1720224
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Macro Letters
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 11; Journal ID: ISSN 2161-1653
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Li, Wei, Carrillo, Jan-Michael Y., Sumpter, Bobby G., and Kumar, Rajeev. Modulating Microphase Separation of Lamellae-Forming Diblock Copolymers via Ionic Junctions. United States: N. p., 2020.
Web. doi:10.1021/acsmacrolett.0c00592.
Li, Wei, Carrillo, Jan-Michael Y., Sumpter, Bobby G., & Kumar, Rajeev. Modulating Microphase Separation of Lamellae-Forming Diblock Copolymers via Ionic Junctions. United States. https://doi.org/10.1021/acsmacrolett.0c00592
Li, Wei, Carrillo, Jan-Michael Y., Sumpter, Bobby G., and Kumar, Rajeev. Fri .
"Modulating Microphase Separation of Lamellae-Forming Diblock Copolymers via Ionic Junctions". United States. https://doi.org/10.1021/acsmacrolett.0c00592. https://www.osti.gov/servlets/purl/1720224.
@article{osti_1720224,
title = {Modulating Microphase Separation of Lamellae-Forming Diblock Copolymers via Ionic Junctions},
author = {Li, Wei and Carrillo, Jan-Michael Y. and Sumpter, Bobby G. and Kumar, Rajeev},
abstractNote = {In this work, we present a molecular dynamics simulation study investigating the phase behavior of lamellae-forming diblock copolymers with a single ionic junction on the backbone. Our results show qualitative agreement with experimental findings regarding enhanced microphase separation with the introduction of an ionic junction at the conjunction point, while further revealing nonmonotonic changes in domain spacing and order–disorder transition as a function of the electrostatic interaction strength. This highlights the dominant roles of entropic and binding effects of counterions under weak and strong ionic correlations, respectively. The location of the ionic junction is found to effectively modulate the charge distribution and chain conformation in the ordered domains; its presence in the middle of a block promotes folding of the block, leading to a smaller domain size. These findings demonstrate the interplay of ionic coupling with steric hindrance and chain end effects, which enhances our understanding of the delicate control over the microphase domain features.},
doi = {10.1021/acsmacrolett.0c00592},
journal = {ACS Macro Letters},
number = 11,
volume = 9,
place = {United States},
year = {Fri Oct 30 00:00:00 EDT 2020},
month = {Fri Oct 30 00:00:00 EDT 2020}
}
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Works referenced in this record:
Polymer Electrolytes
journal, July 2013
- Hallinan, Daniel T.; Balsara, Nitash P.
- Annual Review of Materials Research, Vol. 43, Issue 1
Harnessing the Power of Plastics: Nanostructured Polymer Systems in Lithium-Ion Batteries
journal, August 2017
- Morris, Melody A.; An, Hyosung; Lutkenhaus, Jodie L.
- ACS Energy Letters, Vol. 2, Issue 8
Dielectric and Viscoelastic Responses of Imidazolium-Based Ionomers with Different Counterions and Side Chain Lengths
journal, January 2014
- Choi, U. Hyeok; Ye, Yuesheng; Salas de la Cruz, David
- Macromolecules, Vol. 47, Issue 2
Effect of Polymer Architecture and Ionic Aggregation on the Scattering Peak in Model Ionomers
journal, March 2011
- Hall, Lisa M.; Stevens, Mark J.; Frischknecht, Amalie L.
- Physical Review Letters, Vol. 106, Issue 12
Ionic Aggregate Structure in Ionomer Melts: Effect of Molecular Architecture on Aggregates and the Ionomer Peak
journal, December 2011
- Hall, Lisa M.; Seitz, Michelle E.; Winey, Karen I.
- Journal of the American Chemical Society, Vol. 134, Issue 1
Ionic Correlations in Random Ionomers
journal, February 2018
- Ma, Boran; Nguyen, Trung Dac; Pryamitsyn, Victor A.
- ACS Nano, Vol. 12, Issue 3
Theory of polyelectrolytes in solutions and at surfaces
journal, November 2005
- Dobrynin, A.; Rubinstein, M.
- Progress in Polymer Science, Vol. 30, Issue 11
Computer Simulations of Ion Transport in Polymer Electrolyte Membranes
journal, June 2016
- Mogurampelly, Santosh; Borodin, Oleg; Ganesan, Venkat
- Annual Review of Chemical and Biomolecular Engineering, Vol. 7, Issue 1
Influence of Dielectric Constant on Ionic Transport in Polyether-Based Electrolytes
journal, November 2017
- Wheatle, Bill K.; Keith, Jordan R.; Mogurampelly, Santosh
- ACS Macro Letters, Vol. 6, Issue 12
Polymerized Ionic Liquids: The Effect of Random Copolymer Composition on Ion Conduction
journal, July 2009
- Chen, Hong; Choi, Jae-Hong; Salas-de la Cruz, David
- Macromolecules, Vol. 42, Issue 13
Polymerized Ionic Liquids with Enhanced Static Dielectric Constants
journal, January 2013
- Choi, U. Hyeok; Mittal, Anuj; Price, Terry L.
- Macromolecules, Vol. 46, Issue 3
Mechanisms Underlying Ion Transport in Polymerized Ionic Liquids
journal, July 2017
- Mogurampelly, Santosh; Keith, Jordan R.; Ganesan, Venkat
- Journal of the American Chemical Society, Vol. 139, Issue 28
Influence of Counterion Structure on Conductivity of Polymerized Ionic Liquids
journal, March 2019
- Keith, Jordan R.; Rebello, Nathan J.; Cowen, Benjamin J.
- ACS Macro Letters, Vol. 8, Issue 4
Effect of Molecular Weight on the Mechanical and Electrical Properties of Block Copolymer Electrolytes
journal, June 2007
- Singh, Mohit; Odusanya, Omolola; Wilmes, Gregg M.
- Macromolecules, Vol. 40, Issue 13
Effect of Molecular Weight and Salt Concentration on Conductivity of Block Copolymer Electrolytes
journal, July 2009
- Panday, Ashoutosh; Mullin, Scott; Gomez, Enrique D.
- Macromolecules, Vol. 42, Issue 13
Effect of Ion Distribution on Conductivity of Block Copolymer Electrolytes
journal, March 2009
- Gomez, Enrique D.; Panday, Ashoutosh; Feng, Edward H.
- Nano Letters, Vol. 9, Issue 3
Thermodynamic Properties of Block Copolymer Electrolytes Containing Imidazolium and Lithium Salts
journal, October 2010
- Wanakule, Nisita S.; Virgili, Justin M.; Teran, Alexander A.
- Macromolecules, Vol. 43, Issue 19
Mechanisms Underlying Ion Transport in Lamellar Block Copolymer Membranes
journal, March 2012
- Ganesan, Venkat; Pyramitsyn, Victor; Bertoni, Colleen
- ACS Macro Letters, Vol. 1, Issue 4
Ordering Transition in Salt-Doped Diblock Copolymers
journal, April 2016
- Qin, Jian; de Pablo, Juan J.
- Macromolecules, Vol. 49, Issue 9
Ion Distribution in Microphase-Separated Copolymers with Periodic Dielectric Permittivity
journal, February 2018
- Chu, Weiwei; Qin, Jian; de Pablo, Juan J.
- Macromolecules, Vol. 51, Issue 5
Role of Solvation on Diffusion of Ions in Diblock Copolymers: Understanding the Molecular Weight Effect through Modeling
journal, October 2019
- Seo, Youngmi; Shen, Kuan-Hsuan; Brown, Jonathan R.
- Journal of the American Chemical Society, Vol. 141, Issue 46
Field-Theoretic Study of Salt-Induced Order and Disorder in a Polarizable Diblock Copolymer
journal, July 2019
- Grzetic, Douglas J.; Delaney, Kris T.; Fredrickson, Glenn H.
- ACS Macro Letters, Vol. 8, Issue 8
Microphase Separation of Ionic Liquid-Containing Diblock Copolymers: Effects of Dielectric Inhomogeneity and Asymmetry in the Molecular Volumes and Interactions between the Cation and Anion
journal, May 2020
- Nakamura, Issei
- Macromolecules, Vol. 53, Issue 10
Intrinsic Ion Transport Properties of Block Copolymer Electrolytes
journal, June 2020
- Sharon, Daniel; Bennington, Peter; Dolejsi, Moshe
- ACS Nano, Vol. 14, Issue 7
Microphase separation of charged diblock copolymers: melts and solutions
journal, September 1992
- Marko, J. F.; Rabin, Y.
- Macromolecules, Vol. 25, Issue 5
Microphase separation in polyelectrolytic diblock copolymer melt: Weak segregation limit
journal, June 2007
- Kumar, Rajeev; Muthukumar, M.
- The Journal of Chemical Physics, Vol. 126, Issue 21
Phase Behavior of Symmetric Sulfonated Block Copolymers
journal, May 2008
- Park, Moon Jeong; Balsara, Nitash P.
- Macromolecules, Vol. 41, Issue 10
Electrostatic control of block copolymer morphology
journal, June 2014
- Sing, Charles E.; Zwanikken, Jos W.; Olvera de la Cruz, Monica
- Nature Materials, Vol. 13, Issue 7
Electrostatically Tuned Microdomain Morphology and Phase-Dependent Ion Transport Anisotropy in Single-Ion Conducting Block Copolyelectrolytes
journal, June 2018
- Zhai, Chenxi; Zhou, Huanhuan; Gao, Teng
- Macromolecules, Vol. 51, Issue 12
Diffusion in Lamellae, Cylinders, and Double Gyroid Block Copolymer Nanostructures
journal, August 2018
- Shen, Kuan-Hsuan; Brown, Jonathan R.; Hall, Lisa M.
- ACS Macro Letters, Vol. 7, Issue 9
Nanoscale Resolution of Electric-field Induced Motion in Ionic Diblock Copolymer Thin Films
journal, September 2018
- Dugger, Jason W.; Li, Wei; Chen, Mingtao
- ACS Applied Materials & Interfaces, Vol. 10, Issue 38
Mechanisms of Ion Transport in Block Copolymeric Polymerized Ionic Liquids
journal, August 2019
- Zhang, Zidan; Krajniak, Jakub; Keith, Jordan R.
- ACS Macro Letters, Vol. 8, Issue 9
Morphologies of block copolymers composed of charged and neutral blocks
journal, January 2012
- Wang, Xiaojun; Goswami, Monojoy; Kumar, Rajeev
- Soft Matter, Vol. 8, Issue 11
Polymers with Complex Architecture by Living Anionic Polymerization
journal, December 2001
- Hadjichristidis, Nikos; Pitsikalis, Marinos; Pispas, Stergios
- Chemical Reviews, Vol. 101, Issue 12
Supramolecular Engineering with Macromolecules: An Alternative Concept for Block Copolymers
journal, October 2002
- Lohmeijer, Bas G. G.; Schubert, Ulrich S.
- Angewandte Chemie International Edition, Vol. 41, Issue 20
‘Click’ Chemistry in Polymer and Materials Science
journal, January 2007
- Binder, Wolfgang H.; Sachsenhofer, Robert
- Macromolecular Rapid Communications, Vol. 28, Issue 1
Click Chemistry in Materials Science
journal, January 2014
- Xi, Weixian; Scott, Timothy F.; Kloxin, Christopher J.
- Advanced Functional Materials, Vol. 24, Issue 18
End-Group Chemistry and Junction Chemistry in Polymer Science: Past, Present, and Future
journal, January 2020
- Kim, Jihoon; Jung, Ha Young; Park, Moon Jeong
- Macromolecules, Vol. 53, Issue 3
Melt Morphology of Polystyrene−Poly(ethylene oxide) Metallo-Supramolecular Diblock Copolymer
journal, November 2003
- Al-Hussein, M.; Lohmeijer, B. G. G.; Schubert, U. S.
- Macromolecules, Vol. 36, Issue 25
Phase Behavior of the Melt of Polystyrene−Poly(ethylene oxide) Metallo-Supramolecular Diblock Copolymer with Bulky Counterions
journal, April 2005
- Al-Hussein, M.; de Jeu, W. H.; Lohmeijer, B. G. G.
- Macromolecules, Vol. 38, Issue 7
Enhanced Block Copolymer Phase Separation Using Click Chemistry and Ionic Junctions
journal, November 2015
- Luo, Yingdong; Montarnal, Damien; Treat, Nicolas J.
- ACS Macro Letters, Vol. 4, Issue 12
Self-Assembly of Ionizable “Clicked” P3HT- b -PMMA Copolymers: Ionic Bonding Group/Counterion Effects on Morphology
journal, December 2016
- Ji, Eunkyung; Pellerin, Virginie; Rubatat, Laurent
- Macromolecules, Vol. 50, Issue 1
High χ–Low N Block Polymers: How Far Can We Go?
journal, September 2015
- Sinturel, Christophe; Bates, Frank S.; Hillmyer, Marc A.
- ACS Macro Letters, Vol. 4, Issue 9
Statistical field theory description of inhomogeneous polarizable soft matter
journal, October 2016
- Martin, Jonathan M.; Li, Wei; Delaney, Kris T.
- The Journal of Chemical Physics, Vol. 145, Issue 15
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
Two-Step Chemical Transformation of Polystyrene- block -poly(solketal acrylate) Copolymers for Increasing χ
journal, August 2019
- Yu, Duk Man; Smith, Darren M.; Kim, Hyeyoung
- Macromolecules, Vol. 52, Issue 17
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
Effect of Tapering on Morphology and Interfacial Behavior of Diblock Copolymers from Molecular Dynamics Simulations
journal, July 2015
- Seo, Youngmi; Brown, Jonathan R.; Hall, Lisa M.
- Macromolecules, Vol. 48, Issue 14
Molecular dynamics study on microstructures of diblock copolymer melts with soft potential and potential recovery
journal, September 2016
- Ryu, Ji Ho; Wee, Han Sol; Lee, Won Bo
- Physical Review E, Vol. 94, Issue 3
Fluctuation in electrolyte solutions: The self energy
journal, February 2010
- Wang, Zhen-Gang
- Physical Review E, Vol. 81, Issue 2
Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995
- Plimpton, Steve
- Journal of Computational Physics, Vol. 117, Issue 1
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
Implementing molecular dynamics on hybrid high performance computers – Particle–particle particle-mesh
journal, March 2012
- Brown, W. Michael; Kohlmeyer, Axel; Plimpton, Steven J.
- Computer Physics Communications, Vol. 183, Issue 3
Role of Repulsive Forces in Determining the Equilibrium Structure of Simple Liquids
journal, June 1971
- Weeks, John D.; Chandler, David; Andersen, Hans C.
- The Journal of Chemical Physics, Vol. 54, Issue 12
Collective and Single-Chain Correlations in Disordered Melts of Symmetric Diblock Copolymers: Quantitative Comparison of Simulations and Theory
journal, January 2014
- Glaser, Jens; Qin, Jian; Medapuram, Pavani
- Macromolecules, Vol. 47, Issue 2
Reduction of Line Edge Roughness of Polystyrene- block -Poly(methyl methacrylate) Copolymer Nanopatterns By Introducing Hydrogen Bonding at the Junction Point of Two Block Chains
journal, February 2017
- Lee, Kyu Seong; Lee, Jaeyong; Kwak, Jongheon
- ACS Applied Materials & Interfaces, Vol. 9, Issue 37
Theory of block copolymer interfaces in the strong segregation limit
journal, November 1993
- Semenov, A. N.
- Macromolecules, Vol. 26, Issue 24
Salt Doping in PEO-Containing Block Copolymers: Counterion and Concentration Effects
journal, April 2009
- Young, Wen-Shiue; Epps, Thomas H.
- Macromolecules, Vol. 42, Issue 7
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
Theory of block copolymer solutions: nonselective good solvents
journal, March 1989
- Fredrickson, Glenn H.; Leibler, Ludwik
- Macromolecules, Vol. 22, Issue 3
Competitive Interactions of π–π Junctions and Their Role on Microphase Separation of Chiral Block Copolymers
journal, May 2017
- Wen, Tao; Lee, Jing-Yu; Li, Ming-Chia
- Chemistry of Materials, Vol. 29, Issue 10