Direct comparisons of X-ray scattering and atomistic molecular dynamics simulations for precise acid copolymers and ionomers
Abstract
Designing acid- and ion-containing polymers for optimal proton, ion, or water transport would benefit profoundly from predictive models or theories that relate polymer structures with ionomer morphologies. Recently, atomistic molecular dynamics (MD) simulations were performed to study the morphologies of precise poly(ethylene-co-acrylic acid) copolymer and ionomer melts. Here, we present the first direct comparisons between scattering profiles, I(q), calculated from these atomistic MD simulations and experimental X-ray data for 11 materials. This set of precise polymers has spacers of exactly 9, 15, or 21 carbons between acid groups and has been partially neutralized with Li, Na, Cs, or Zn. In these polymers, the simulations at 120 °C reveal ionic aggregates with a range of morphologies, from compact, isolated aggregates (type 1) to branched, stringy aggregates (type 2) to branched, stringy aggregates that percolate through the simulation box (type 3). Excellent agreement is found between the simulated and experimental scattering peak positions across all polymer types and aggregate morphologies. The shape of the amorphous halo in the simulated I(q) profile is in excellent agreement with experimental I(q). We found that the modified hard-sphere scattering model fits both the simulation and experimental I(q) data for type 1 aggregate morphologies, and the aggregatemore »
- Authors:
-
- Univ. of Pennsylvania, Philadelphia, PA (United States)
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Univ. of Florida, Gainesville, FL (United States)
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1235257
- Report Number(s):
- SAND-2015-0362J
Journal ID: ISSN 0024-9297; 562236
- Grant/Contract Number:
- AC04-94AL85000
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Macromolecules
- Additional Journal Information:
- Journal Volume: 48; Journal ID: ISSN 0024-9297
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Buitrago, C. Francisco, Bolintineanu, Dan, Seitz, Michelle E., Opper, Kathleen L., Wagener, Kenneth B., Stevens, Mark J., Frischknecht, Amalie Lucile, and Winey, Karen I. Direct comparisons of X-ray scattering and atomistic molecular dynamics simulations for precise acid copolymers and ionomers. United States: N. p., 2015.
Web. doi:10.1021/ma5022117.
Buitrago, C. Francisco, Bolintineanu, Dan, Seitz, Michelle E., Opper, Kathleen L., Wagener, Kenneth B., Stevens, Mark J., Frischknecht, Amalie Lucile, & Winey, Karen I. Direct comparisons of X-ray scattering and atomistic molecular dynamics simulations for precise acid copolymers and ionomers. United States. https://doi.org/10.1021/ma5022117
Buitrago, C. Francisco, Bolintineanu, Dan, Seitz, Michelle E., Opper, Kathleen L., Wagener, Kenneth B., Stevens, Mark J., Frischknecht, Amalie Lucile, and Winey, Karen I. 2015.
"Direct comparisons of X-ray scattering and atomistic molecular dynamics simulations for precise acid copolymers and ionomers". United States. https://doi.org/10.1021/ma5022117. https://www.osti.gov/servlets/purl/1235257.
@article{osti_1235257,
title = {Direct comparisons of X-ray scattering and atomistic molecular dynamics simulations for precise acid copolymers and ionomers},
author = {Buitrago, C. Francisco and Bolintineanu, Dan and Seitz, Michelle E. and Opper, Kathleen L. and Wagener, Kenneth B. and Stevens, Mark J. and Frischknecht, Amalie Lucile and Winey, Karen I.},
abstractNote = {Designing acid- and ion-containing polymers for optimal proton, ion, or water transport would benefit profoundly from predictive models or theories that relate polymer structures with ionomer morphologies. Recently, atomistic molecular dynamics (MD) simulations were performed to study the morphologies of precise poly(ethylene-co-acrylic acid) copolymer and ionomer melts. Here, we present the first direct comparisons between scattering profiles, I(q), calculated from these atomistic MD simulations and experimental X-ray data for 11 materials. This set of precise polymers has spacers of exactly 9, 15, or 21 carbons between acid groups and has been partially neutralized with Li, Na, Cs, or Zn. In these polymers, the simulations at 120 °C reveal ionic aggregates with a range of morphologies, from compact, isolated aggregates (type 1) to branched, stringy aggregates (type 2) to branched, stringy aggregates that percolate through the simulation box (type 3). Excellent agreement is found between the simulated and experimental scattering peak positions across all polymer types and aggregate morphologies. The shape of the amorphous halo in the simulated I(q) profile is in excellent agreement with experimental I(q). We found that the modified hard-sphere scattering model fits both the simulation and experimental I(q) data for type 1 aggregate morphologies, and the aggregate sizes and separations are in agreement. Given the stringy structure in types 2 and 3, we develop a scattering model based on cylindrical aggregates. Both the spherical and cylindrical scattering models fit I(q) data from the polymers with type 2 and 3 aggregates equally well, and the extracted aggregate radii and inter- and intra-aggregate spacings are in agreement between simulation and experiment. Furthermore, these dimensions are consistent with real-space analyses of the atomistic MD simulations. By combining simulations and experiments, the ionomer scattering peak can be associated with the average distance between branches of type 2 or 3 aggregates. Furthermore, this direct comparison of X-ray scattering data to the atomistic MD simulations is a substantive step toward providing a comprehensive, predictive model for ionomer morphology, gives substantial support for this atomistic MD model, and provides new credibility to the presence of stringy, branched, and percolated ionic aggregates in precise ionomer melts.},
doi = {10.1021/ma5022117},
url = {https://www.osti.gov/biblio/1235257},
journal = {Macromolecules},
issn = {0024-9297},
number = ,
volume = 48,
place = {United States},
year = {Mon Feb 09 00:00:00 EST 2015},
month = {Mon Feb 09 00:00:00 EST 2015}
}
Web of Science
Works referenced in this record:
Review and critical analysis of the morphology of random ionomers across many length scales
journal, June 2008
- Grady, Brian P.
- Polymer Engineering & Science, Vol. 48, Issue 6
Atomistic Simulations Predict a Surprising Variety of Morphologies in Precise Ionomers
journal, February 2013
- Bolintineanu, Dan S.; Stevens, Mark J.; Frischknecht, Amalie L.
- ACS Macro Letters, Vol. 2, Issue 3
Influence of Cation Type on Ionic Aggregates in Precise Ionomers
journal, June 2013
- Bolintineanu, Dan S.; Stevens, Mark J.; Frischknecht, Amalie L.
- Macromolecules, Vol. 46, Issue 13
Synthesis and Morphology of Well-Defined Poly(ethylene- co -acrylic acid) Copolymers
journal, September 2007
- Baughman, Travis W.; Chan, Christopher D.; Winey, Karen I.
- Macromolecules, Vol. 40, Issue 18
Nanoscale Morphology in Precisely Sequenced Poly(ethylene- co -acrylic acid) Zinc Ionomers
journal, June 2010
- Seitz, Michelle E.; Chan, Christopher D.; Opper, Kathleen L.
- Journal of the American Chemical Society, Vol. 132, Issue 23
Precision Phosphonic Acid Functionalized Polyolefin Architectures
journal, April 2010
- Opper, Kathleen L.; Markova, Dilyana; Klapper, Markus
- Macromolecules, Vol. 43, Issue 8
Precision Ionomers: Synthesis and Thermal/Mechanical Characterization
journal, January 2012
- Aitken, Brian S.; Buitrago, C. Francisco; Heffley, Jason D.
- Macromolecules, Vol. 45, Issue 2
Crystallization of Polyethylenes Containing Chlorines: Precise vs Random Placement
journal, October 2008
- Alamo, R. G.; Jeon, K.; Smith, R. L.
- Macromolecules, Vol. 41, Issue 19
Synthesis and Crystallization of Precision ADMET Polyolefins Containing Halogens
journal, June 2006
- Boz, Emine; Wagener, Kenneth B.; Ghosal, Anindya
- Macromolecules, Vol. 39, Issue 13
Morphological Trends in Precise Acid- and Ion-Containing Polyethylenes at Elevated Temperature
journal, November 2013
- Buitrago, C. Francisco; Alam, Todd M.; Opper, Kathleen L.
- Macromolecules, Vol. 46, Issue 22
Microstructure of ionomers: interpretation of small-angle x-ray scattering data
journal, December 1983
- Yarusso, David J.; Cooper, Stuart L.
- Macromolecules, Vol. 16, Issue 12
Analysis of SAXS data from ionomer systems
journal, March 1985
- Yarusso, D. J.; Cooper, S. L.
- Polymer, Vol. 26, Issue 3
Hard-sphere interactions between spherical domains in diblock copolymers
journal, September 1984
- Kinning, David J.; Thomas, Edwin L.
- Macromolecules, Vol. 17, Issue 9
Anomalous small-angle x-ray scattering from a sulfonated polystyrene ionomer
journal, November 1988
- Ding, Y. Samuel; Hubbard, Stevan R.; Hodgson, Keith O.
- Macromolecules, Vol. 21, Issue 6
Nanoscale Morphology of Poly(styrene- ran -methacrylic acid) Ionomers: The Role of Preparation Method, Thermal Treatment, and Acid Copolymer Structure
journal, May 2007
- Benetatos, Nicholas M.; Winey, Karen I.
- Macromolecules, Vol. 40, Issue 9
Counterion Effect on the Rheology and Morphology of Tailored Poly(dimethylsiloxane) Ionomers
journal, February 2006
- Batra, Ashish; Cohen, Claude; Kim, Hansoo
- Macromolecules, Vol. 39, Issue 4
Ionic aggregates in Zn- and Na-neutralized poly(ethylene-ran-methacrylic acid) blown films
journal, January 2005
- Benetatos, Nicholas M.; Winey, Karen I.
- Journal of Polymer Science Part B: Polymer Physics, Vol. 43, Issue 24
Deconvolution of scanning transmission electron microscopy images of ionomers
journal, January 2003
- Kirkmeyer, Brian P.; Puetter, Richard C.; Yahil, Amos
- Journal of Polymer Science Part B: Polymer Physics, Vol. 41, Issue 4
Spherical and vesicular ionic aggregates in Zn-neutralized sulfonated polystyrene ionomers
journal, January 2001
- Kirkmeyer, Brian P.; Weiss, Robert A.; Winey, Karen I.
- Journal of Polymer Science Part B: Polymer Physics, Vol. 39, Issue 5
Ionic Aggregates in Partially Zn-Neutralized Poly(ethylene- r an -methacrylic acid) Ionomers: Shape, Size, and Size Distribution
journal, January 2000
- Winey, Karen I.; Laurer, Jonathan H.; Kirkmeyer, Brian P.
- Macromolecules, Vol. 33, Issue 2
Imaging and X-ray Microanalysis of a Poly(ethylene- ran -methacrylic acid) Ionomer Melt Neutralized with Sodium
journal, September 2002
- Taubert, Andreas; Winey, Karen I.
- Macromolecules, Vol. 35, Issue 19
Vesicular Ionic Aggregates in Poly(styrene- r an -methacrylic acid) Ionomers Neutralized with Cs
journal, March 2002
- Kirkmeyer, Brian P.; Taubert, Andreas; Kim, Joon-Seop
- Macromolecules, Vol. 35, Issue 7
Bicontinuous Morphologies in Homologous Multiblock Copolymers and Their Homopolymer Blends
journal, October 1998
- Laurer, Jonathan H.; Hajduk, Damian A.; Dreckötter, Stefan
- Macromolecules, Vol. 31, Issue 21
Quantitative Morphology Study of Cu-Neutralized Poly(styrene- ran -methacrylic acid) Ionomers: STEM Imaging, X-ray Scattering, and Real-Space Structural Modeling
journal, February 2007
- Benetatos, Nicholas M.; Chan, Christopher D.; Winey, Karen I.
- Macromolecules, Vol. 40, Issue 4
Reconciling STEM and X-ray Scattering Data To Determine the Nanoscale Ionic Aggregate Morphology in Sulfonated Polystyrene Ionomers
journal, August 2008
- Zhou, Nancy C.; Chan, Christopher D.; Winey, Karen I.
- Macromolecules, Vol. 41, Issue 16
Influence of the Degree of Sulfonation on the Structure and Dynamics of Sulfonated Polystyrene Copolymers
journal, December 2010
- Castagna, Alicia M.; Wang, Wenqin; Winey, Karen I.
- Macromolecules, Vol. 43, Issue 24
Structure and Dynamics of Zinc-Neutralized Sulfonated Polystyrene Ionomers
journal, April 2011
- Castagna, Alicia M.; Wang, Wenqin; Winey, Karen I.
- Macromolecules, Vol. 44, Issue 8
Influence of Cation Type on Structure and Dynamics in Sulfonated Polystyrene Ionomers
journal, July 2011
- Castagna, Alicia M.; Wang, Wenqin; Winey, Karen I.
- Macromolecules, Vol. 44, Issue 13
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
Cation Coordination and Motion in a Poly(ethylene oxide)-Based Single Ion Conductor
journal, July 2012
- Lin, Kan-Ju; Maranas, Janna K.
- Macromolecules, Vol. 45, Issue 15
Does decreasing ion–ion association improve cation mobility in single ion conductors?
journal, January 2013
- Lin, Kan-Ju; Maranas, Janna K.
- Physical Chemistry Chemical Physics, Vol. 15, Issue 38
Scaling behavior and local structure of ion aggregates in single-ion conductors
journal, January 2014
- Lu, Keran; Rudzinski, Joseph F.; Noid, W. G.
- Soft Matter, Vol. 10, Issue 7
Hydrogen-bonded aggregates in precise acid copolymers
journal, February 2014
- Lueth, Christopher A.; Bolintineanu, Dan S.; Stevens, Mark J.
- The Journal of Chemical Physics, Vol. 140, Issue 5
Structure and Dynamics of Coarse-Grained Ionomer Melts in an External Electric Field
journal, January 2015
- Ting, Christina L.; Stevens, Mark J.; Frischknecht, Amalie L.
- Macromolecules, Vol. 48, Issue 3
Dynamics of Model Ionomer Melts of Various Architectures
journal, September 2012
- Hall, Lisa M.; Stevens, Mark J.; Frischknecht, Amalie L.
- Macromolecules, Vol. 45, Issue 19
Room Temperature Morphologies of Precise Acid- and Ion-Containing Polyethylenes
journal, November 2013
- Buitrago, C. Francisco; Jenkins, Janelle E.; Opper, Kathleen L.
- Macromolecules, Vol. 46, Issue 22
Analysis of small-angle scattering data from colloids and polymer solutions: modeling and least-squares fitting
journal, July 1997
- Pedersen, Jan Skov
- Advances in Colloid and Interface Science, Vol. 70
Size and Shape of Micelles Studied by Means of SANS, PCS, and FCS
journal, March 2010
- Gapiński, Jacek; Szymański, Jȩdrzej; Wilk, Agnieszka
- Langmuir, Vol. 26, Issue 12
Scattering from Short Stiff Cylindrical Micelles Formed by Fully Ionized TDAO in NaCl/Water Solutions
journal, April 2003
- Garamus, Vasil M.; Pedersen, Jan Skov; Maeda, Hiroshi
- Langmuir, Vol. 19, Issue 9
Statistical Mechanics of Rodlike Particles. II. A Scaled Particle Investigation of the Aligned→Isotropic Transition in a Fluid of Rigid Spherocylinders
journal, February 1970
- Cotter, Martha A.; Martire, Daniel E.
- The Journal of Chemical Physics, Vol. 52, Issue 4
Works referencing / citing this record:
Structure/property relationships in copolymers comprising renewable isosorbide, glucarodilactone, and 2,5-bis(hydroxymethyl)furan subunits
journal, January 2017
- Lillie, Leon M.; Tolman, William B.; Reineke, Theresa M.
- Polymer Chemistry, Vol. 8, Issue 24
Designing tougher elastomers with ionomers
journal, October 2017
- Winey, Karen I.
- Science, Vol. 358, Issue 6362
The evolution of acidic and ionic aggregates in ionomers during microsecond simulations
journal, February 2019
- Frischknecht, Amalie L.; Winey, Karen I.
- The Journal of Chemical Physics, Vol. 150, Issue 6
Impact of ion content and electric field on mechanical properties of coarse-grained ionomers
journal, October 2018
- Sampath, Janani; Hall, Lisa M.
- The Journal of Chemical Physics, Vol. 149, Issue 16
Toughening elastomers using mussel-inspired iron-catechol complexes
journal, October 2017
- Filippidi, Emmanouela; Cristiani, Thomas R.; Eisenbach, Claus D.
- Science, Vol. 358, Issue 6362
Precision Polyelectrolytes with Phenylsulfonic Acid Branches at Every Five Carbons
journal, May 2018
- Kendrick, Aaron; Neary, William J.; Delgado, Jose D.
- Macromolecular Rapid Communications, Vol. 39, Issue 14
Impact of ionic aggregate structure on ionomer mechanical properties from coarse-grained molecular dynamics simulations
journal, October 2017
- Sampath, Janani; Hall, Lisa M.
- The Journal of Chemical Physics, Vol. 147, Issue 13
Evaluation of nano- and mesoscale structural features in composite materials through hierarchical decomposition of the radial distribution function
journal, February 2018
- García-Negrón, Valerie; Oyedele, Akinola D.; Ponce, Eduardo
- Journal of Applied Crystallography, Vol. 51, Issue 1