Manipulating the ABCs of self-assembly via low-χ block polymer design
Abstract
Block polymer self-assembly typically translates molecular chain connectivity into mesoscale structure by exploiting incompatible blocks with large interaction parameters (χij). In this report, we demonstrate that the converse approach, encoding low-χ interactions in ABC bottlebrush triblock terpolymers (χAC ≲ 0), promotes organization into a unique mixed-domain lamellar morphology which we designate LAMP. Transmission electron microscopy indicates that LAMP exhibits ACBC domain connectivity, in contrast to conventional three-domain lamellae (LAM3) with ABCB periods. Complementary small angle X-ray scattering experiments reveal a strongly decreasing domain spacing with increasing total molar mass. Self-consistent field theory reinforces these observations and predicts that LAMP is thermodynamically stable below a critical χAC, above which LAM3 emerges. Both experiments and theory expose close analogies to ABA triblock copolymer phase behavior, collectively suggesting that low-χ interactions between chemically similar or distinct blocks intimately influence self-assembly. Furthermore, these conclusions provide new opportunities in block polymer design with potential consequences spanning all self-assembling soft materials.
- Authors:
-
[2];
[6];
[1]
- Arnold and Mabel Beckman Laboratories for Chemical Synthesis, California Institute of Technology, Pasadena, CA 91125,
- Materials Department, University of California, Santa Barbara, CA 93106,, Department of Chemical Engineering, University of California, Santa Barbara, CA 93106,
- X-Ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, IL 60439,
- Department of Materials Science, California Institute of Technology, Pasadena, CA 91125,
- Electrochemical Technologies Group, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA 91109,
- Department of Chemical Engineering, University of Waterloo, Waterloo, ON N2L 3G1, Canada,, Department of Physics &, Astronomy, University of Waterloo, Waterloo, ON N2L 3G1, Canada,, Waterloo Institute for Nanotechnology, University of Waterloo, Waterloo, ON N2L 3G1, Canada
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- National Science Foundation (NSF); U.S. Department of Defense (DOD); USDOE Office of Science (SC)
- OSTI Identifier:
- 1361566
- Alternate Identifier(s):
- OSTI ID: 1373730
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Published Article
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- Additional Journal Information:
- Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 114 Journal Issue: 25; Journal ID: ISSN 0027-8424
- Publisher:
- Proceedings of the National Academy of Sciences
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; LAMP; block polymer; domain spacing; polymer nanostructure; self-assembly
Citation Formats
Chang, Alice B., Bates, Christopher M., Lee, Byeongdu, Garland, Carol M., Jones, Simon C., Spencer, Russell K. W., Matsen, Mark W., and Grubbs, Robert H. Manipulating the ABCs of self-assembly via low-χ block polymer design. United States: N. p., 2017.
Web. doi:10.1073/pnas.1701386114.
Chang, Alice B., Bates, Christopher M., Lee, Byeongdu, Garland, Carol M., Jones, Simon C., Spencer, Russell K. W., Matsen, Mark W., & Grubbs, Robert H. Manipulating the ABCs of self-assembly via low-χ block polymer design. United States. https://doi.org/10.1073/pnas.1701386114
Chang, Alice B., Bates, Christopher M., Lee, Byeongdu, Garland, Carol M., Jones, Simon C., Spencer, Russell K. W., Matsen, Mark W., and Grubbs, Robert H. Tue .
"Manipulating the ABCs of self-assembly via low-χ block polymer design". United States. https://doi.org/10.1073/pnas.1701386114.
@article{osti_1361566,
title = {Manipulating the ABCs of self-assembly via low-χ block polymer design},
author = {Chang, Alice B. and Bates, Christopher M. and Lee, Byeongdu and Garland, Carol M. and Jones, Simon C. and Spencer, Russell K. W. and Matsen, Mark W. and Grubbs, Robert H.},
abstractNote = {Block polymer self-assembly typically translates molecular chain connectivity into mesoscale structure by exploiting incompatible blocks with large interaction parameters (χij). In this report, we demonstrate that the converse approach, encoding low-χ interactions in ABC bottlebrush triblock terpolymers (χAC ≲ 0), promotes organization into a unique mixed-domain lamellar morphology which we designate LAMP. Transmission electron microscopy indicates that LAMP exhibits ACBC domain connectivity, in contrast to conventional three-domain lamellae (LAM3) with ABCB periods. Complementary small angle X-ray scattering experiments reveal a strongly decreasing domain spacing with increasing total molar mass. Self-consistent field theory reinforces these observations and predicts that LAMP is thermodynamically stable below a critical χAC, above which LAM3 emerges. Both experiments and theory expose close analogies to ABA triblock copolymer phase behavior, collectively suggesting that low-χ interactions between chemically similar or distinct blocks intimately influence self-assembly. Furthermore, these conclusions provide new opportunities in block polymer design with potential consequences spanning all self-assembling soft materials.},
doi = {10.1073/pnas.1701386114},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 25,
volume = 114,
place = {United States},
year = {Tue Jun 06 00:00:00 EDT 2017},
month = {Tue Jun 06 00:00:00 EDT 2017}
}
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https://doi.org/10.1073/pnas.1701386114
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