Self-assembly and structural relaxation in a model ionomer melt

Goswami, Monojoy; Borreguero, Jose M.; Sumpter, Bobby G.

doi:10.1063/1.4913517

Self-assembly and structural relaxation in a model ionomer melt

Journal Article · Thu Feb 26 00:00:00 EST 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4913517· OSTI ID:1286814

Goswami, Monojoy ^[1]; Borreguero, Jose M. ^[2]; Sumpter, Bobby G. ^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Material Sciences and Computer Science and Mathematics Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Data Analysis & Visualization Division

Molecular dynamics simulations are used to understand the self-assembly and structural relaxation in ionomer melts containing less than 10% degree of ionization on the backbone. We study the self-assembly of charged sites and counterions that show structural ordering and agglomeration with a range of structures that can be achieved by changing the dielectric constant of the medium. The intermediate scattering function shows a decoupling of charge and counterion relaxation at longer length scales for only high dielectric constant and at shorter length scales for all dielectric constants. Finally, the slow structural decay of counterions in the strongly correlated ionomer system closely resembles transport properties of semi-flexible polymers.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1286814

Alternate ID(s):: OSTI ID: 1228554

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 8 Vol. 142; ISSN JCPSA6; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

References (55)

Sassena — X-ray and neutron scattering calculated from molecular dynamics trajectories using massively parallel computers Lindner, Benjamin; Smith, Jeremy C. Computer Physics Communications, Vol. 183, Issue 7 https://doi.org/10.1016/j.cpc.2012.02.010	journal	July 2012
Performance enhancement of direct ethanol fuel cell using Nafion composites with high volume fraction of titania Matos, B. R.; Isidoro, R. A.; Santiago, E. I. Journal of Power Sources, Vol. 268 https://doi.org/10.1016/j.jpowsour.2014.06.097	journal	December 2014
Study of gas permeabilities through polystyrene-block-poly(ethylene oxide) copolymers Minelli, Matteo; Giacinti Baschetti, Marco; Hallinan, Daniel T. Journal of Membrane Science, Vol. 432 https://doi.org/10.1016/j.memsci.2012.12.038	journal	April 2013
Enhancement on proton conductivity of inorganic–organic composite electrolyte membrane by addition of sulfonic acid group Munakata, Hirokazu; Chiba, Hiroto; Kanamura, Kiyoshi Solid State Ionics, Vol. 176, Issue 31-34 https://doi.org/10.1016/j.ssi.2005.03.027	journal	October 2005
Relation between structural and conductivity relaxation in PEO and PEO based electrolytes K. Money, Benson; Hariharan, K.; Swenson, J. Solid State Ionics, Vol. 262 https://doi.org/10.1016/j.ssi.2013.09.033	journal	September 2014
Conduction in Polymers: Dynamic Disorder Transport Nitzan, Abraham; Ratner, Mark A. The Journal of Physical Chemistry, Vol. 98, Issue 7 https://doi.org/10.1021/j100058a009	journal	February 1994
Nanoscale Morphology in Precisely Sequenced Poly(ethylene- co -acrylic acid) Zinc Ionomers Seitz, Michelle E.; Chan, Christopher D.; Opper, Kathleen L. Journal of the American Chemical Society, Vol. 132, Issue 23 https://doi.org/10.1021/ja101991d	journal	June 2010
Thermally Driven Ionic Aggregation in Poly(ethylene oxide)-Based Sulfonate Ionomers Wang, Wenqin; Tudryn, Gregory J.; Colby, Ralph H. Journal of the American Chemical Society, Vol. 133, Issue 28 https://doi.org/10.1021/ja201405v	journal	July 2011
Ionic Aggregate Structure in Ionomer Melts: Effect of Molecular Architecture on Aggregates and the Ionomer Peak Hall, Lisa M.; Seitz, Michelle E.; Winey, Karen I. Journal of the American Chemical Society, Vol. 134, Issue 1 https://doi.org/10.1021/ja209142b	journal	December 2011
Crystallization in Sequence-Defined Peptoid Diblock Copolymers Induced by Microphase Separation Sun, Jing; Teran, Alexander A.; Liao, Xunxun Journal of the American Chemical Society, Vol. 136, Issue 5 https://doi.org/10.1021/ja412123y	journal	January 2014
Molecular Dynamics Simulation of Microstructure and Molecular Mobilities in Swollen Nafion Membranes Vishnyakov, Aleksey; Neimark, Alexander V. The Journal of Physical Chemistry B, Vol. 105, Issue 39 https://doi.org/10.1021/jp0102567	journal	October 2001
LiTFSI Structure and Transport in Ethylene Carbonate from Molecular Dynamics Simulations Borodin, Oleg; Smith, Grant D. The Journal of Physical Chemistry B, Vol. 110, Issue 10 https://doi.org/10.1021/jp056249q	journal	March 2006
Structure and Dynamics of N -Methyl- N -propylpyrrolidinium Bis(trifluoromethanesulfonyl)imide Ionic Liquid from Molecular Dynamics Simulations Borodin, Oleg; Smith, Grant D. The Journal of Physical Chemistry B, Vol. 110, Issue 23 https://doi.org/10.1021/jp061593o	journal	June 2006
Li ⁺ Transport in Lithium Sulfonylimide−Oligo(ethylene oxide) Ionic Liquids and Oligo(ethylene oxide) Doped with LiTFSI Borodin, Oleg; Smith, G. D.; Geiculescu, Olt The Journal of Physical Chemistry B, Vol. 110, Issue 47 https://doi.org/10.1021/jp0653104	journal	November 2006
Breakdown of Inverse Morphologies in Charged Diblock Copolymers Goswami, Monojoy; Kumar, Rajeev; Sumpter, Bobby G. The Journal of Physical Chemistry B, Vol. 115, Issue 13 https://doi.org/10.1021/jp111001n	journal	April 2011
Ion Hopping in Ethylene−Methacrylic Acid Ionomer Melts As Probed by Rheometry and Cation Diffusion Measurements Tierney, Neena K.; Register, Richard A. Macromolecules, Vol. 35, Issue 6 https://doi.org/10.1021/ma011775a	journal	March 2002
Mechanism of Ion Transport in Amorphous Poly(ethylene oxide)/LiTFSI from Molecular Dynamics Simulations Borodin, Oleg; Smith, Grant D. Macromolecules, Vol. 39, Issue 4 https://doi.org/10.1021/ma052277v	journal	February 2006
Computer Simulations of Ionomer Self-Assembly and Dynamics Goswami, Monojoy; Kumar, Sanat K.; Bhattacharya, Aniket Macromolecules, Vol. 40, Issue 12 https://doi.org/10.1021/ma070074w	journal	June 2007
Counterion Dynamics in Polyester−Sulfonate Ionomers with Ionic Liquid Counterions Tudryn, Gregory J.; Liu, Wenjuan; Wang, Shih-Wa Macromolecules, Vol. 44, Issue 9 https://doi.org/10.1021/ma102547q	journal	May 2011
Decoupling Ionic Conductivity from Structural Relaxation: A Way to Solid Polymer Electrolytes? Agapov, A. L.; Sokolov, A. P. Macromolecules, Vol. 44, Issue 11 https://doi.org/10.1021/ma2001096	journal	June 2011
Cation Coordination and Motion in a Poly(ethylene oxide)-Based Single Ion Conductor Lin, Kan-Ju; Maranas, Janna K. Macromolecules, Vol. 45, Issue 15 https://doi.org/10.1021/ma300716h	journal	July 2012
Dynamics of Model Ionomer Melts of Various Architectures Hall, Lisa M.; Stevens, Mark J.; Frischknecht, Amalie L. Macromolecules, Vol. 45, Issue 19 https://doi.org/10.1021/ma301308n	journal	September 2012
Phase Behavior of Ionic Block Copolymers Studied by a Minimal Lattice Model with Short-Range Interactions Knychała, P.; Dzięcielski, M.; Banaszak, M. Macromolecules, Vol. 46, Issue 14 https://doi.org/10.1021/ma400078y	journal	July 2013
How Does Nanoscale Crystalline Structure Affect Ion Transport in Solid Polymer Electrolytes? Cheng, Shan; Smith, Derrick M.; Li, Christopher Y. Macromolecules, Vol. 47, Issue 12 https://doi.org/10.1021/ma500734q	journal	June 2014
Synthesis and Characterization of Ureidopyrimidone Telechelics by CuAAC “Click” Reaction: Effect of T _g and Polarity Bobade, Sachin; Wang, Yangyang; Mays, Jimmy Macromolecules, Vol. 47, Issue 15 https://doi.org/10.1021/ma5007705	journal	July 2014
Clustering of Ions in Organic Polymers. A Theoretical Approach Eisenberg, A. Macromolecules, Vol. 3, Issue 2 https://doi.org/10.1021/ma60014a006	journal	March 1970
Phase Behavior of Symmetric Sulfonated Block Copolymers Park, Moon Jeong; Balsara, Nitash P. Macromolecules, Vol. 41, Issue 10 https://doi.org/10.1021/ma702733f	journal	May 2008
Understanding the Lithium Transport within a Rouse-Based Model for a PEO/LiTFSI Polymer Electrolyte Diddens, Diddo; Heuer, Andreas; Borodin, Oleg Macromolecules, Vol. 43, Issue 4 https://doi.org/10.1021/ma901893h	journal	February 2010
Anisotropic Proton Conduction in Aligned Block Copolymer Electrolyte Membranes at Equilibrium with Humid Air Park, Moon Jeong; Balsara, Nitash P. Macromolecules, Vol. 43, Issue 1 https://doi.org/10.1021/ma901980b	journal	January 2010
Lithium Ion Transport Mechanism in Ternary Polymer Electrolyte-Ionic Liquid Mixtures: A Molecular Dynamics Simulation Study Diddens, Diddo; Heuer, Andreas ACS Macro Letters, Vol. 2, Issue 4 https://doi.org/10.1021/mz3006457	journal	March 2013
Morphology and Thermodynamic Properties of a Copolymer with an Electronically Conducting Block: Poly(3-ethylhexylthiophene)- block -poly(ethylene oxide) Patel, Shrayesh N.; Javier, Anna E.; Beers, Keith M. Nano Letters, Vol. 12, Issue 9 https://doi.org/10.1021/nl302454c	journal	January 2012
Electrochemically Oxidized Electronic and Ionic Conducting Nanostructured Block Copolymers for Lithium Battery Electrodes Patel, Shrayesh N.; Javier, Anna E.; Balsara, Nitash P. ACS Nano, Vol. 7, Issue 7 https://doi.org/10.1021/nn4018685	journal	June 2013
Detection of subsurface structures underneath dendrites formed on cycled lithium metal electrodes Harry, Katherine J.; Hallinan, Daniel T.; Parkinson, Dilworth Y. Nature Materials, Vol. 13, Issue 1 https://doi.org/10.1038/nmat3793	journal	November 2013
Electrostatic control of block copolymer morphology Sing, Charles E.; Zwanikken, Jos W.; Olvera de la Cruz, Monica Nature Materials, Vol. 13, Issue 7 https://doi.org/10.1038/nmat4001	journal	June 2014
Tunable morphologies from charged block copolymers Goswami, Monojoy; Sumpter, Bobby G.; Huang, Tianzi Soft Matter, Vol. 6, Issue 24 https://doi.org/10.1039/c0sm00733a	journal	January 2010
Effects of backbone rigidity on the local structure and dynamics in polymer melts and glasses Kumar, Rajeev; Goswami, Monojoy; Sumpter, Bobby G. Physical Chemistry Chemical Physics, Vol. 15, Issue 13 https://doi.org/10.1039/c3cp43737j	journal	January 2013
Decoupling charge transport from the structural dynamics in room temperature ionic liquids Griffin, Philip; Agapov, Alexander L.; Kisliuk, Alexander The Journal of Chemical Physics, Vol. 135, Issue 11 https://doi.org/10.1063/1.3638269	journal	September 2011
Molecular dynamics simulation of a polymer chain in solution Dünweg, Burkhard; Kremer, Kurt The Journal of Chemical Physics, Vol. 99, Issue 9 https://doi.org/10.1063/1.465445	journal	November 1993
Proton conductivity of perfluorosulfonate ionomers at high temperature and high relative humidity Matos, Bruno R.; Goulart, Cleverson A.; Santiago, Elisabete I. Applied Physics Letters, Vol. 104, Issue 9 https://doi.org/10.1063/1.4867351	journal	March 2014
Algorithms for macromolecular dynamics and constraint dynamics van Gunsteren, W. F.; Berendsen, H. J. C. Molecular Physics, Vol. 34, Issue 5 https://doi.org/10.1080/00268977700102571	journal	November 1977
Algorithms for brownian dynamics van Gunsteren, W. F.; Berendsen, H. J. C. Molecular Physics, Vol. 45, Issue 3 https://doi.org/10.1080/00268978200100491	journal	February 1982
Simulation of Electrostatic Systems in Periodic Boundary Conditions. I. Lattice Sums and Dielectric Constants de Leeuw, S. W.; Perram, J. W.; Smith, E. R. Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 373, Issue 1752 https://doi.org/10.1098/rspa.1980.0135	journal	October 1980
Molecular dynamics simulation for polymers in the presence of a heat bath Grest, Gary S.; Kremer, Kurt Physical Review A, Vol. 33, Issue 5 https://doi.org/10.1103/PhysRevA.33.3628	journal	May 1986
Anomalous diffusion of a tethered membrane: A Monte Carlo investigation Popova, Hristina; Milchev, Andrey Physical Review E, Vol. 77, Issue 4 https://doi.org/10.1103/PhysRevE.77.041906	journal	April 2008
Anomalous chain diffusion in polymer nanocomposites for varying polymer-filler interaction strengths Goswami, Monojoy; Sumpter, Bobby G. Physical Review E, Vol. 81, Issue 4 https://doi.org/10.1103/PhysRevE.81.041801	journal	April 2010
Resolving the Mystery of the Chain Friction Mechanism in Polymer Liquids Sokolov, Alexei P.; Schweizer, Kenneth S. Physical Review Letters, Vol. 102, Issue 24 https://doi.org/10.1103/PhysRevLett.102.248301	journal	June 2009
Effect of Polymer Architecture and Ionic Aggregation on the Scattering Peak in Model Ionomers Hall, Lisa M.; Stevens, Mark J.; Frischknecht, Amalie L. Physical Review Letters, Vol. 106, Issue 12 https://doi.org/10.1103/PhysRevLett.106.127801	journal	March 2011
Decoupling of Ionic Transport from Segmental Relaxation in Polymer Electrolytes Wang, Yangyang; Agapov, Alexander L.; Fan, Fei Physical Review Letters, Vol. 108, Issue 8 https://doi.org/10.1103/PhysRevLett.108.088303	journal	February 2012
Cation Transport in Polymer Electrolytes: A Microscopic Approach Maitra, A.; Heuer, A. Physical Review Letters, Vol. 98, Issue 22 https://doi.org/10.1103/PhysRevLett.98.227802	journal	May 2007
Polymer Electrolytes Hallinan, Daniel T.; Balsara, Nitash P. Annual Review of Materials Research, Vol. 43, Issue 1 https://doi.org/10.1146/annurev-matsci-071312-121705	journal	July 2013
Synthesis of Li[sup +] Ion Conductive PEO-PSt Block Copolymer Electrolyte with Microphase Separation Structure Niitani, Takeshi; Shimada, Mikiya; Kawamura, Kiyoshi Electrochemical and Solid-State Letters, Vol. 8, Issue 8 https://doi.org/10.1149/1.1940491	journal	January 2005
Star-Shaped Polymer Electrolyte with Microphase Separation Structure for All-Solid-State Lithium Batteries Niitani, Takeshi; Amaike, Masato; Nakano, Hiroyuki Journal of The Electrochemical Society, Vol. 156, Issue 7 https://doi.org/10.1149/1.3129245	journal	January 2009
Lithium Metal Stability in Batteries with Block Copolymer Electrolytes Hallinan, Daniel T.; Mullin, Scott A.; Stone, Gregory M. Journal of The Electrochemical Society, Vol. 160, Issue 3 https://doi.org/10.1149/2.030303jes	journal	January 2013
Anomalous Diffusion and Relaxation of Collapsed Polymer Chains Milchev, A.; Binder, K. Europhysics Letters (EPL), Vol. 26, Issue 9 https://doi.org/10.1209/0295-5075/26/9/006	journal	June 1994
Driven polymer translocation through a nanopore: A manifestation of anomalous diffusion Dubbeldam, J. L. A.; Milchev, A.; Rostiashvili, V. G. Europhysics Letters (EPL), Vol. 79, Issue 1 https://doi.org/10.1209/0295-5075/79/18002	journal	June 2007

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