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

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

doi:10.1073/pnas.1701386114

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

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

Research output: Contribution to journal › Article › peer-review

48 Scopus citations

Abstract

Block polymer self-assembly typically translates molecular chain connectivity into mesoscale structure by exploiting incompatible blocks with large interaction parameters (χ_ij). In this article, 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 LAM_P 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. These conclusions provide fresh opportunities for block polymer design with potential consequences spanning all self-assembling soft materials.

Original language	English (US)
Pages (from-to)	6462-6467
Number of pages	6
Journal	Proceedings of the National Academy of Sciences of the United States of America
Volume	114
Issue number	25
DOIs	https://doi.org/10.1073/pnas.1701386114
State	Published - Jun 20 2017
Externally published	Yes

Bibliographical note

Funding Information:
The authors thank M. S. Ladinsky for assistance with ultramicrotomy, as well as M. T. Irwin, S. Chanpuriya, and T. Li for helpful discussions about sample preparation and TEM. The authors gratefully acknowledge helpful discussions with F. S. Bates and Z.-G. Wang. This work was supported by the National Science Foundation through Grant CHE-1502616. A.B.C. thanks the US Department of Defense for support through the National Defense Science and Engineering Graduate (NDSEG) Fellowship. C.M.B. thanks the Dreyfus Foundation for Environmental Postdoctoral Fellowship EP-13-142 and the University of California, Santa Barbara for funding. This research used resources of the Advanced Photon Source, a US Department of Energy Office of Science User Facility operated by Argonne National Laboratory under Contract DE-AC02-06CH11357.

Keywords

Block polymer
Domain spacing
LAM
Polymer nanostructure
Self-assembly

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title = "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 article, 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. These conclusions provide fresh opportunities for block polymer design with potential consequences spanning all self-assembling soft materials.",

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note = "Funding Information: The authors thank M. S. Ladinsky for assistance with ultramicrotomy, as well as M. T. Irwin, S. Chanpuriya, and T. Li for helpful discussions about sample preparation and TEM. The authors gratefully acknowledge helpful discussions with F. S. Bates and Z.-G. Wang. This work was supported by the National Science Foundation through Grant CHE-1502616. A.B.C. thanks the US Department of Defense for support through the National Defense Science and Engineering Graduate (NDSEG) Fellowship. C.M.B. thanks the Dreyfus Foundation for Environmental Postdoctoral Fellowship EP-13-142 and the University of California, Santa Barbara for funding. This research used resources of the Advanced Photon Source, a US Department of Energy Office of Science User Facility operated by Argonne National Laboratory under Contract DE-AC02-06CH11357.",

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AU - Bates, Christopher M.

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AU - Jones, Simon C.

AU - Spencer, Russell K.W.

AU - Matsen, Mark W.

AU - Grubbs, Robert H.

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N2 - Block polymer self-assembly typically translates molecular chain connectivity into mesoscale structure by exploiting incompatible blocks with large interaction parameters (χij). In this article, 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. These conclusions provide fresh opportunities for block polymer design with potential consequences spanning all self-assembling soft materials.

AB - Block polymer self-assembly typically translates molecular chain connectivity into mesoscale structure by exploiting incompatible blocks with large interaction parameters (χij). In this article, 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. These conclusions provide fresh opportunities for block polymer design with potential consequences spanning all self-assembling soft materials.

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

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Keywords

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