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

Ryan, Justin J.; Mineart, Kenneth P.; Lee, Byeongdu; Spontak, Richard J.

doi:10.1002/admi.201701667

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:

Ryan, Justin J. ^[1]; Mineart, Kenneth P. ^[2]; Lee, Byeongdu ^[3];

^[4]

North Carolina State Univ., Raleigh, NC (United States)
Bucknell Univ., Lewisburg, PA (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
North Carolina State Univ., Raleigh, NC (United States); Humboldt-Univ. zu Berlin, Berlin (Germany)

Publication Date:: 2018-02-09

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.

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                    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

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                    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.

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@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}

}

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Journal Article:

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https://doi.org/10.1002/admi.201701667

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Figures / Tables:

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 referencing / citing this record:

Electrochemical Manipulation of Aligned Block Copolymer Templates
journal, November 2019

Liu, Sherri S. Y.; Ludwigs, Sabine
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Similar Records

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

Abstract

Citation Formats

Figures / Tables:

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

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

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

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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

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

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

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

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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

Orthorhombic Fddd Network in Diblock Copolymer Melts journal, June 2007

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

Block Copolymers for Fuel Cells journal, January 2011

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

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

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

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

Mechanochromic Photonic Gels journal, June 2013

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

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

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

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

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Block Copolymers for Organic Optoelectronics journal, December 2009

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

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

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Electrochemical Manipulation of Aligned Block Copolymer Templates journal, November 2019

Bicomponent Block Copolymers Derived from One or More Random Copolymers as an Alternative Route to Controllable Phase Behavior
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Systematic Study on the Effect of Solvent Removal Rate on the Morphology of Solvent Vapor Annealed ABA Triblock Copolymer Thin Films
journal, December 2011

Morphological Investigation of Midblock-Sulfonated Block Ionomers Prepared from Solvents Differing in Polarity
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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

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

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

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

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

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

Orthorhombic Fddd Network in Diblock Copolymer Melts
journal, June 2007

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

Block Copolymers for Fuel Cells
journal, January 2011

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Block Copolymers for Organic Optoelectronics
journal, December 2009

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

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

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

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

Universal Phenomenology of Symmetric Diblock Copolymers near the Order–Disorder Transition
journal, January 2015

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

Electrochemical Manipulation of Aligned Block Copolymer Templates
journal, November 2019