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Title: Ordering and Grain Growth in Charged Block Copolymer Bulk Films: A Comparison of Solvent-Related Processes

Abstract

While prior efforts have demonstrated that the morphologies of block copolymer (BC) bulk films can be controlled through judicious chemical design and thermal annealing, recent interest has focused on regulating the orientation of BC nanostructures and minimizing defects. Thermal processes developed to achieve this purpose for nonpolar BCs are not, however, suitable for orienting microphase-ordered BCs composed of at least one block with charged moieties that can form thermally stable ionic clusters. To overcome this challenge, we have previously applied solvent-vapor (SV) annealing to block ionomer (BI) bulk films composed of midblock-sulfonated pentablock copolymers and established that this approach yields highly ordered morphologies that display evidence of improved in-plane orientation. Here, we employ small-angle X-ray scattering to compare the effectiveness of three solvent-related processes-SV annealing, SV permeation, and SV sorption-on BI ordering and grain growth, and offer explanations for observed differences on the basis of thermodynamic- and transport-related considerations. As a result, differences in the experimental design of these solvent-related processes are found to affect nanostructural development, as evidenced by the extent of in-plane grain growth.

Authors:
 [1];  [2];  [3]; ORCiD logo [4]
  1. North Carolina State Univ., Raleigh, NC (United States)
  2. Bucknell Univ., Lewisburg, PA (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. North Carolina State Univ., Raleigh, NC (United States); Humboldt-Univ. zu Berlin, Berlin (Germany)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
Nonwovens Institute (NWI); Freudenberg Group - Performance Materials; German Research Foundation (DFG); Bucknell University; USDOE
OSTI Identifier:
1461339
Alternate Identifier(s):
OSTI ID: 1419992
Grant/Contract Number:  
AC02-06CH11357; DE‐AC02‐06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Materials Interfaces
Additional Journal Information:
Journal Volume: 5; Journal Issue: 8; Journal ID: ISSN 2196-7350
Publisher:
Wiley-VCH
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; block ionomers; lamellar orientation; solvent permeation; solvent-vapor annealing; thermoplastic elastomers

Citation Formats

Ryan, Justin J., Mineart, Kenneth P., Lee, Byeongdu, and Spontak, Richard J.. Ordering and Grain Growth in Charged Block Copolymer Bulk Films: A Comparison of Solvent-Related Processes. United States: N. p., 2018. Web. https://doi.org/10.1002/admi.201701667.
Ryan, Justin J., Mineart, Kenneth P., Lee, Byeongdu, & Spontak, Richard J.. Ordering and Grain Growth in Charged Block Copolymer Bulk Films: A Comparison of Solvent-Related Processes. United States. https://doi.org/10.1002/admi.201701667
Ryan, Justin J., Mineart, Kenneth P., Lee, Byeongdu, and Spontak, Richard J.. Fri . "Ordering and Grain Growth in Charged Block Copolymer Bulk Films: A Comparison of Solvent-Related Processes". United States. https://doi.org/10.1002/admi.201701667. https://www.osti.gov/servlets/purl/1461339.
@article{osti_1461339,
title = {Ordering and Grain Growth in Charged Block Copolymer Bulk Films: A Comparison of Solvent-Related Processes},
author = {Ryan, Justin J. and Mineart, Kenneth P. and Lee, Byeongdu and Spontak, Richard J.},
abstractNote = {While prior efforts have demonstrated that the morphologies of block copolymer (BC) bulk films can be controlled through judicious chemical design and thermal annealing, recent interest has focused on regulating the orientation of BC nanostructures and minimizing defects. Thermal processes developed to achieve this purpose for nonpolar BCs are not, however, suitable for orienting microphase-ordered BCs composed of at least one block with charged moieties that can form thermally stable ionic clusters. To overcome this challenge, we have previously applied solvent-vapor (SV) annealing to block ionomer (BI) bulk films composed of midblock-sulfonated pentablock copolymers and established that this approach yields highly ordered morphologies that display evidence of improved in-plane orientation. Here, we employ small-angle X-ray scattering to compare the effectiveness of three solvent-related processes-SV annealing, SV permeation, and SV sorption-on BI ordering and grain growth, and offer explanations for observed differences on the basis of thermodynamic- and transport-related considerations. As a result, differences in the experimental design of these solvent-related processes are found to affect nanostructural development, as evidenced by the extent of in-plane grain growth.},
doi = {10.1002/admi.201701667},
journal = {Advanced Materials Interfaces},
number = 8,
volume = 5,
place = {United States},
year = {2018},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Figures / Tables:

Scheme 1 Scheme 1: Chemical structure of the sulfonated block ionomer (SBI) composed of tert-butylstyrene (T), ethylene-alt-propylene (EP) and styrene-co-styrenesulfonate (S/sS) blocks.

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Works referenced in this record:

Bicomponent Block Copolymers Derived from One or More Random Copolymers as an Alternative Route to Controllable Phase Behavior
journal, June 2017

  • Ashraf, Arman R.; Ryan, Justin J.; Satkowski, Michael M.
  • Macromolecular Rapid Communications, Vol. 38, Issue 17
  • DOI: 10.1002/marc.201700207

Systematic Study on the Effect of Solvent Removal Rate on the Morphology of Solvent Vapor Annealed ABA Triblock Copolymer Thin Films
journal, December 2011

  • Albert, Julie N. L.; Young, Wen-Shiue; Lewis, Ronald L.
  • ACS Nano, Vol. 6, Issue 1
  • DOI: 10.1021/nn203776c

Morphological Investigation of Midblock-Sulfonated Block Ionomers Prepared from Solvents Differing in Polarity
journal, December 2014

  • Mineart, Kenneth P.; Jiang, Xi; Jinnai, Hiroshi
  • Macromolecular Rapid Communications, Vol. 36, Issue 5
  • DOI: 10.1002/marc.201400627

Multiblock Polymers: Panacea or Pandora's Box?
journal, April 2012


Characterization of a sulfonated pentablock copolymer for desalination applications
journal, November 2010


Ternary Phase Behavior of a Triblock Copolymer in the Presence of an Endblock-Selective Homopolymer and a Midblock-Selective Oil
journal, July 2012

  • Krishnan, Arjun S.; Smith, Steven D.; Spontak, Richard J.
  • Macromolecules, Vol. 45, Issue 15
  • DOI: 10.1021/ma300417u

Study of oriented block copolymers films obtained by roll-casting
journal, September 2002


Directed self-assembly of block copolymers: a tutorial review of strategies for enabling nanotechnology with soft matter
journal, January 2014

  • Hu, Hanqiong; Gopinadhan, Manesh; Osuji, Chinedum O.
  • Soft Matter, Vol. 10, Issue 22
  • DOI: 10.1039/c3sm52607k

The Full Phase Behavior for Block Copolymers in Solvents of Varying Selectivity
journal, June 2002

  • Lodge, Timothy P.; Pudil, Bryant; Hanley, Kenneth J.
  • Macromolecules, Vol. 35, Issue 12
  • DOI: 10.1021/ma0200975

A double helical structure formed from an amorphous, achiral ABC triblock terpolymer
journal, January 2009

  • Jinnai, Hiroshi; Kaneko, Takeshi; Matsunaga, Kazuyuki
  • Soft Matter, Vol. 5, Issue 10
  • DOI: 10.1039/b901008d

Highly Oriented and Ordered Arrays from Block Copolymers via Solvent Evaporation
journal, February 2004

  • Kim, S. H.; Misner, M. J.; Xu, T.
  • Advanced Materials, Vol. 16, Issue 3, p. 226-231
  • DOI: 10.1002/adma.200304906

Directed self-assembly of block copolymers for next generation nanolithography
journal, December 2013


Quantitative evaluation of orientation in cellulose fibres from the X-ray fibre diagram
journal, January 1946

  • Hermans, J. J.; Hermans, P. H.; Vermaas, D.
  • Recueil des Travaux Chimiques des Pays-Bas, Vol. 65, Issue 6
  • DOI: 10.1002/recl.19460650605

Orthorhombic Fddd Network in Diblock Copolymer Melts
journal, June 2007

  • Takenaka, Mikihito; Wakada, Tsutomu; Akasaka, Satoshi
  • Macromolecules, Vol. 40, Issue 13
  • DOI: 10.1021/ma070739u

The Gyroid: A New Equilibrium Morphology in Weakly Segregated Diblock Copolymers
journal, July 1994

  • Hajduk, Damian A.; Harper, Paul E.; Gruner, Sol M.
  • Macromolecules, Vol. 27, Issue 15
  • DOI: 10.1021/ma00093a006

Block Copolymers for Fuel Cells
journal, January 2011

  • Elabd, Yossef A.; Hickner, Michael A.
  • Macromolecules, Vol. 44, Issue 1
  • DOI: 10.1021/ma101247c

Highly Flexible Aqueous Photovoltaic Elastomer Gels Derived from Sulfonated Block Ionomers
journal, January 2015

  • Al-Mohsin, Heba A.; Mineart, Kenneth P.; Spontak, Richard J.
  • Advanced Energy Materials, Vol. 5, Issue 8
  • DOI: 10.1002/aenm.201401941

High-Modulus, High-Conductivity Nanostructured Polymer Electrolyte Membranes via Polymerization-Induced Phase Separation
journal, December 2013

  • Schulze, Morgan W.; McIntosh, Lucas D.; Hillmyer, Marc A.
  • Nano Letters, Vol. 14, Issue 1
  • DOI: 10.1021/nl4034818

Anisotropy and Transport in Poly(arylene ether sulfone) Hydrophilic−Hydrophobic Block Copolymers
journal, January 2010

  • Hou, Jianbo; Li, Jing; Madsen, Louis A.
  • Macromolecules, Vol. 43, Issue 1
  • DOI: 10.1021/ma902070h

A mini-review on anion exchange membranes for fuel cell applications: Stability issue and addressing strategies
journal, June 2015


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


Block Copolymers—Designer Soft Materials
journal, February 1999

  • Bates, Frank S.; Fredrickson, Glenn H.
  • Physics Today, Vol. 52, Issue 2
  • DOI: 10.1063/1.882522

Structure–property relationship in sulfonated pentablock copolymers
journal, March 2012


Monodisperse cylindrical micelles by crystallization-driven living self-assembly
journal, May 2010

  • Gilroy, Joe B.; Gädt, Torben; Whittell, George R.
  • Nature Chemistry, Vol. 2, Issue 7
  • DOI: 10.1038/nchem.664

Morphology and transport properties of midblock-sulfonated triblock copolymers
journal, January 2010

  • Moore, Hunter D.; Saito, Tomonori; Hickner, Michael A.
  • Journal of Materials Chemistry, Vol. 20, Issue 30
  • DOI: 10.1039/c0jm00068j

Effect of Architecture on the Phase Behavior of AB-Type Block Copolymer Melts
journal, February 2012


50th Anniversary Perspective : Block Polymers—Pure Potential
journal, December 2016


Mechanochromic Photonic Gels
journal, June 2013

  • Chan, Edwin P.; Walish, Joseph J.; Urbas, Augustine M.
  • Advanced Materials, Vol. 25, Issue 29
  • DOI: 10.1002/adma.201300692

A Solvent-Vapor Approach toward the Control of Block Ionomer Morphologies
journal, April 2016


Microfibres and macroscopic films from the coordination-driven hierarchical self-assembly of cylindrical micelles
journal, August 2016

  • Lunn, David J.; Gould, Oliver E. C.; Whittell, George R.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms12371

Phase Behavior of Block Copolymer/Homopolymer Blends
journal, August 1995


Spontaneous Perpendicular Orientation of Cylindrical Microdomains in a Block Copolymer Thick Film
journal, March 2009

  • Sakurai, Shinichi; Bando, Hiromichi; Yoshida, Hidekazu
  • Macromolecules, Vol. 42, Issue 6
  • DOI: 10.1021/ma900155n

Solvent-Templated Block Ionomers for Base- and Acid-Gas Separations: Effect of Humidity on Ammonia and Carbon Dioxide Permeation
journal, September 2017

  • Ansaloni, Luca; Dai, Zhongde; Ryan, Justin J.
  • Advanced Materials Interfaces, Vol. 4, Issue 22
  • DOI: 10.1002/admi.201700854

Hydrothermal Conditioning of Physical Hydrogels Prepared from a Midblock-Sulfonated Multiblock Copolymer
journal, January 2017

  • Mineart, Kenneth P.; Dickerson, Joshua D.; Love, Dillon M.
  • Macromolecular Rapid Communications, Vol. 38, Issue 5
  • DOI: 10.1002/marc.201600666

Enhanced Biomimetic Performance of Ionic Polymer-Metal Composite Actuators Prepared with Nanostructured Block Ionomers
journal, November 2011

  • Vargantwar, Pruthesh H.; Roskov, Kristen E.; Ghosh, Tushar K.
  • Macromolecular Rapid Communications, Vol. 33, Issue 1
  • DOI: 10.1002/marc.201100535

Preface to Forum on Block Copolymers for Nanotechnology Applications
journal, March 2017


Alignment of Self-Assembled Structures in Block Copolymer Films by Solvent Vapor Permeation
journal, April 2010


Phase Behavior of Symmetric Sulfonated Block Copolymers
journal, May 2008

  • Park, Moon Jeong; Balsara, Nitash P.
  • Macromolecules, Vol. 41, Issue 10
  • DOI: 10.1021/ma702733f

Block Copolymers for Organic Optoelectronics
journal, December 2009

  • Segalman, Rachel A.; McCulloch, Bryan; Kirmayer, Saar
  • Macromolecules, Vol. 42, Issue 23
  • DOI: 10.1021/ma901350w

Large-Scale Roll-to-Roll Fabrication of Vertically Oriented Block Copolymer Thin Films
journal, May 2013

  • Singh, Gurpreet; Batra, Saurabh; Zhang, Ren
  • ACS Nano, Vol. 7, Issue 6
  • DOI: 10.1021/nn401094s

Effect of Composition on the Phase Behavior of Ion-Containing Block Copolymers Studied by a Minimal Lattice Model
journal, March 2014

  • Knychała, P.; Banaszak, M.; Balsara, N. P.
  • Macromolecules, Vol. 47, Issue 7
  • DOI: 10.1021/ma402454j

Structural Color for Additive Manufacturing: 3D-Printed Photonic Crystals from Block Copolymers
journal, February 2017


Structure, physical properties, and molecule transport of gas, liquid, and ions within a pentablock copolymer
journal, August 2014


Water-induced nanochannel networks in self-assembled block ionomers
journal, March 2016

  • Mineart, Kenneth P.; Al-Mohsin, Heba A.; Lee, Byeongdu
  • Applied Physics Letters, Vol. 108, Issue 10
  • DOI: 10.1063/1.4943505

Macroscopic Alignment of Cylinders via Directional Coalescence of Spheres along Annealing Solvent Permeation Directions in Block Copolymer Thick Films
journal, August 2014

  • Cui, Guanghui; Fujikawa, Masamichi; Nagano, Shusaku
  • Macromolecules, Vol. 47, Issue 17
  • DOI: 10.1021/ma501033a

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

Enabling nanotechnology with self assembled block copolymer patterns
journal, October 2003


    Works referencing / citing this record:

    Electrochemical Manipulation of Aligned Block Copolymer Templates
    journal, November 2019

    • Liu, Sherri S. Y.; Ludwigs, Sabine
    • Macromolecular Rapid Communications, Vol. 41, Issue 1
    • DOI: 10.1002/marc.201900485

      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.