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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
Resource Type:
Journal Article: 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. doi: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. doi: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. doi:10.1002/admi.201701667.
@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 = {Fri Feb 09 00:00:00 EST 2018},
month = {Fri Feb 09 00:00:00 EST 2018}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on February 9, 2019
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