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Title: Long-Range Lamellar Alignment in Diblock Bottlebrush Copolymers via Controlled Oscillatory Shear

Abstract

A simple strategy is presented to achieve well-ordered nanostructures in microphase-separated diblock bottlebrush copolymers (dbBB) for potential opportunities in nanotechnology that require large grain sizes and directed orientation. The unique architecture and relaxation processes of dbBBs offer a pathway to enhanced dynamic ordering and reorientation over macroscopic scales. Here, controlled shear is used to align lamellar domains. The high molecular mobility of dbBBs in the melt state, as shown by linear and nonlinear viscoelastic characterization, supports this alignment process. When subjected to large-amplitude oscillatory shear at controlled frequency (ω), strain amplitude (γ), and temperature (Tshear), microphase-separated lamellae transition into highly aligned states as determined by small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). High throughput synchrotron SAXS is used to rapidly characterize microphase separation and lamellar alignment across the entire bulk sample. Lamellae align parallel to shear planes with an orientation order parameter (S) approaching S = 0.8 over a large cubic volume (V ~ mm3).

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1];  [2];  [2];  [1];  [1]
  1. Univ. of Massachusetts, Amherst, MA (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1631925
Report Number(s):
BNL-215966-2020-JAAM
Journal ID: ISSN 0024-9297
Grant/Contract Number:  
SC0012704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 53; Journal Issue: 8; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Scattering; Chemical structure; Order; X-ray scattering; Oscillation

Citation Formats

Yavitt, Benjamin M., Fei, Huafeng, Kopanati, Gayathri, Li, Ruipeng, Fukuto, Masafumi, Winter, H. Henning, and Watkins, James J. Long-Range Lamellar Alignment in Diblock Bottlebrush Copolymers via Controlled Oscillatory Shear. United States: N. p., 2020. Web. doi:10.1021/acs.macromol.0c00047.
Yavitt, Benjamin M., Fei, Huafeng, Kopanati, Gayathri, Li, Ruipeng, Fukuto, Masafumi, Winter, H. Henning, & Watkins, James J. Long-Range Lamellar Alignment in Diblock Bottlebrush Copolymers via Controlled Oscillatory Shear. United States. https://doi.org/10.1021/acs.macromol.0c00047
Yavitt, Benjamin M., Fei, Huafeng, Kopanati, Gayathri, Li, Ruipeng, Fukuto, Masafumi, Winter, H. Henning, and Watkins, James J. 2020. "Long-Range Lamellar Alignment in Diblock Bottlebrush Copolymers via Controlled Oscillatory Shear". United States. https://doi.org/10.1021/acs.macromol.0c00047. https://www.osti.gov/servlets/purl/1631925.
@article{osti_1631925,
title = {Long-Range Lamellar Alignment in Diblock Bottlebrush Copolymers via Controlled Oscillatory Shear},
author = {Yavitt, Benjamin M. and Fei, Huafeng and Kopanati, Gayathri and Li, Ruipeng and Fukuto, Masafumi and Winter, H. Henning and Watkins, James J.},
abstractNote = {A simple strategy is presented to achieve well-ordered nanostructures in microphase-separated diblock bottlebrush copolymers (dbBB) for potential opportunities in nanotechnology that require large grain sizes and directed orientation. The unique architecture and relaxation processes of dbBBs offer a pathway to enhanced dynamic ordering and reorientation over macroscopic scales. Here, controlled shear is used to align lamellar domains. The high molecular mobility of dbBBs in the melt state, as shown by linear and nonlinear viscoelastic characterization, supports this alignment process. When subjected to large-amplitude oscillatory shear at controlled frequency (ω), strain amplitude (γ), and temperature (Tshear), microphase-separated lamellae transition into highly aligned states as determined by small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). High throughput synchrotron SAXS is used to rapidly characterize microphase separation and lamellar alignment across the entire bulk sample. Lamellae align parallel to shear planes with an orientation order parameter (S) approaching S = 0.8 over a large cubic volume (V ~ mm3).},
doi = {10.1021/acs.macromol.0c00047},
url = {https://www.osti.gov/biblio/1631925}, journal = {Macromolecules},
issn = {0024-9297},
number = 8,
volume = 53,
place = {United States},
year = {2020},
month = {4}
}

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