Manipulating the ABCs of self-assembly via low-χ block polymer design

Chang, Alice B.; Bates, Christopher M.; Lee, Byeongdu; Garland, Carol M.; Jones, Simon C.; Spencer, Russell K. W.; Matsen, Mark W.; Grubbs, Robert H.

doi:10.1073/pnas.1701386114

Title: Manipulating the ABCs of self-assembly via low-χ block polymer design

Journal Article · Tue Jun 06 00:00:00 EDT 2017 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1701386114· OSTI ID:1361566

Chang, Alice B. ^[1];

^[2]; Lee, Byeongdu ^[3]; Garland, Carol M. ^[4]; Jones, Simon C. ^[5];

^[6]; Matsen, Mark W. ^[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

Block polymer self-assembly typically translates molecular chain connectivity into mesoscale structure by exploiting incompatible blocks with large interaction parameters (χ_ij). In this report, we demonstrate that the converse approach, encoding low-χ interactions in ABC bottlebrush triblock terpolymers (χ_AC ≲ 0), promotes organization into a unique mixed-domain lamellar morphology which we designate LAM_P. 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 LAM_P is thermodynamically stable below a critical χ_AC, 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.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); U.S. Department of Defense (DOD); USDOE Office of Science (SC)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1361566

Alternate ID(s):: OSTI ID: 1373730

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Vol. 114 Journal Issue: 25; ISSN 0027-8424

Publisher:: Proceedings of the National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 45 works

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