Reevaluation of Poly(ethylene- alt-propylene)- block-Polydimethylsiloxane Phase Behavior Uncovers Topological Close-Packing and Epitaxial Quasicrystal Growth

Aaron P. Lindsay; Ashish Jayaraman; Austin J. Peterson; Andreas J. Mueller; Steven Weigand; Kristoffer Almdal; Mahesh K. Mahanthappa; Timothy P. Lodge; Frank S. Bates

doi:10.1021/acsnano.1c02420

Reevaluation of Poly(ethylene- alt-propylene)- block-Polydimethylsiloxane Phase Behavior Uncovers Topological Close-Packing and Epitaxial Quasicrystal Growth

Aaron P. Lindsay, Ashish Jayaraman, Austin J. Peterson, Andreas J. Mueller, Steven Weigand, Kristoffer Almdal, Mahesh K. Mahanthappa, Timothy P. Lodge, Frank S. Bates

Chemical Engineering and Materials Science

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

18 Scopus citations

Abstract

Reanalysis of an asymmetric poly(ethylene-alt-propylene)-block-polydimethylsiloxane (PEP-PDMS) diblock copolymer first investigated in 1999 has revealed a rich phase behavior including a dodecagonal quasicrystal (DDQC), a Frank-Kasper σ phase, and a body-centered cubic (BCC) packing at high temperature adjacent to the disordered state. On subjecting the sample to large amplitude oscillatory shear well below the σ-BCC order-order transition temperature (TOOT), small-angle X-ray scattering evidenced the emergence of a twinned BCC phase that, on heating, underwent a phase transition to an unusually anisotropic DDQC state. Surprisingly, we observe no evidence of this apparent epitaxy on heating or cooling through the equilibrium σ-BCC transition. We rationalize these results in terms of a shear-induced order-order transition and an apparent BCC-DDQC epitaxy favored by micelle translation-mediated ordering dynamics far below TOOT.

Original language	English (US)
Pages (from-to)	9453-9468
Number of pages	16
Journal	ACS nano
Volume	15
Issue number	6
DOIs	https://doi.org/10.1021/acsnano.1c02420
State	Published - Jun 22 2021

Bibliographical note

Funding Information:
We would like to express our thanks to all the staff at Sector 5 who provided invaluable help in conducting these experiments, keeping science moving forward in spite of the ongoing pandemic. SAXS experiments were performed at the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source (APS). DND-CAT is supported by Northwestern University, The Dow Chemical Company, and DuPont de Nemours, Inc. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Data were collected using an instrument funded by the National Science Foundation under award number 0960140.

Funding Information:
This work was supported by the National Science Foundation under grants no. DMR-1801993 (A.P.L., A.J.M., and F.S.B.) and CHE-1807330 (A.J. and M.K.M.) as well as a National Science Foundation Graduate Research Fellowship under grant no. 00039202 (A.P.L.).

Publisher Copyright:
©

Keywords

block copolymer
epitaxy
quasicrystal
self-assembly
shear orientation
topological close-packing

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Lindsay, A. P., Jayaraman, A., Peterson, A. J., Mueller, A. J., Weigand, S., Almdal, K., Mahanthappa, M. K., Lodge, T. P., & Bates, F. S. (2021). Reevaluation of Poly(ethylene- alt-propylene)- block-Polydimethylsiloxane Phase Behavior Uncovers Topological Close-Packing and Epitaxial Quasicrystal Growth. ACS nano, 15(6), 9453-9468. https://doi.org/10.1021/acsnano.1c02420

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abstract = "Reanalysis of an asymmetric poly(ethylene-alt-propylene)-block-polydimethylsiloxane (PEP-PDMS) diblock copolymer first investigated in 1999 has revealed a rich phase behavior including a dodecagonal quasicrystal (DDQC), a Frank-Kasper σ phase, and a body-centered cubic (BCC) packing at high temperature adjacent to the disordered state. On subjecting the sample to large amplitude oscillatory shear well below the σ-BCC order-order transition temperature (TOOT), small-angle X-ray scattering evidenced the emergence of a twinned BCC phase that, on heating, underwent a phase transition to an unusually anisotropic DDQC state. Surprisingly, we observe no evidence of this apparent epitaxy on heating or cooling through the equilibrium σ-BCC transition. We rationalize these results in terms of a shear-induced order-order transition and an apparent BCC-DDQC epitaxy favored by micelle translation-mediated ordering dynamics far below TOOT.",

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note = "Funding Information: We would like to express our thanks to all the staff at Sector 5 who provided invaluable help in conducting these experiments, keeping science moving forward in spite of the ongoing pandemic. SAXS experiments were performed at the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source (APS). DND-CAT is supported by Northwestern University, The Dow Chemical Company, and DuPont de Nemours, Inc. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Data were collected using an instrument funded by the National Science Foundation under award number 0960140. Funding Information: This work was supported by the National Science Foundation under grants no. DMR-1801993 (A.P.L., A.J.M., and F.S.B.) and CHE-1807330 (A.J. and M.K.M.) as well as a National Science Foundation Graduate Research Fellowship under grant no. 00039202 (A.P.L.). Publisher Copyright: {\textcopyright} ",

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AU - Jayaraman, Ashish

AU - Peterson, Austin J.

AU - Mueller, Andreas J.

AU - Weigand, Steven

AU - Almdal, Kristoffer

AU - Mahanthappa, Mahesh K.

AU - Lodge, Timothy P.

AU - Bates, Frank S.

N1 - Funding Information: We would like to express our thanks to all the staff at Sector 5 who provided invaluable help in conducting these experiments, keeping science moving forward in spite of the ongoing pandemic. SAXS experiments were performed at the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source (APS). DND-CAT is supported by Northwestern University, The Dow Chemical Company, and DuPont de Nemours, Inc. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Data were collected using an instrument funded by the National Science Foundation under award number 0960140. Funding Information: This work was supported by the National Science Foundation under grants no. DMR-1801993 (A.P.L., A.J.M., and F.S.B.) and CHE-1807330 (A.J. and M.K.M.) as well as a National Science Foundation Graduate Research Fellowship under grant no. 00039202 (A.P.L.). Publisher Copyright: ©

PY - 2021/6/22

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N2 - Reanalysis of an asymmetric poly(ethylene-alt-propylene)-block-polydimethylsiloxane (PEP-PDMS) diblock copolymer first investigated in 1999 has revealed a rich phase behavior including a dodecagonal quasicrystal (DDQC), a Frank-Kasper σ phase, and a body-centered cubic (BCC) packing at high temperature adjacent to the disordered state. On subjecting the sample to large amplitude oscillatory shear well below the σ-BCC order-order transition temperature (TOOT), small-angle X-ray scattering evidenced the emergence of a twinned BCC phase that, on heating, underwent a phase transition to an unusually anisotropic DDQC state. Surprisingly, we observe no evidence of this apparent epitaxy on heating or cooling through the equilibrium σ-BCC transition. We rationalize these results in terms of a shear-induced order-order transition and an apparent BCC-DDQC epitaxy favored by micelle translation-mediated ordering dynamics far below TOOT.

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KW - quasicrystal

KW - self-assembly

KW - shear orientation

KW - topological close-packing

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ER -

Reevaluation of Poly(ethylene- alt-propylene)- block-Polydimethylsiloxane Phase Behavior Uncovers Topological Close-Packing and Epitaxial Quasicrystal Growth

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