Frank–Kasper Phases Identified in PDMS-b-PTFEA Copolymers with High Conformational Asymmetry
Abstract
In the search for the formation of Frank–Kasper phases from diblock copolymer self-assembly, a series of compositionally asymmetric poly(dimethylsiloxane)-b-poly(2,2,2-triflouroethyl acrylate)s (PDMS-b-PTFEAs) are synthesized to produce PDMS-rich phases with PDMS volume fractions (ƒPDMS) ranging from 0.746 to 0.869. As determined by small-angle X-ray scattering analysis, the Frank–Kasper σ and C14 phases are identified at ƒPDMS = 0.796 and 0.851, respectively, plausibly due to high conformational asymmetry (ε ≈ 2.20) between the two blocks. Intriguingly, the σ phase develops during heating from a short-range liquid-like packing (LLP) state, whereas the C14 phase is achieved at room temperature, which are both followed by a disordering at higher temperatures. Based on thermal experiments from a super cooled disordered state, the findings further provide compelling evidence of an LLP-hexagonally packed cylinder-σ transition and a direct pathway to the C14 phase during heating from an LLP state.
- Authors:
-
[1]
- Yonsei Univ., Seoul (South Korea). Dept. of Chemical and Biomolecular Engineering
- S. Jeon, T. Jun, S. Jo, Prof. D. Y. RyuDepartment of Chemical and Biomolecular EngineeringYonsei University 50 Yonsei‐ro Seodaemun‐gu Seoul 03722 Korea
- Pohang Univ. of Science and Technology (POSTECH) (Korea, Republic of). Pohang Accelerator Lab.
- Korea Univ., Seoul (South Korea). HU-KIST Graduate School of Converging Science and Technology, and Dept. of Biomicrosystem Technology
- Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- Samsung Electronics, Seoul (South Korea); Samsung Electronics
- OSTI Identifier:
- 1574376
- Alternate Identifier(s):
- OSTI ID: 1607869
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Macromolecular Rapid Communications
- Additional Journal Information:
- Journal Volume: 40; Journal Issue: 19; Journal ID: ISSN 1022-1336
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 42 ENGINEERING; Frank-Kasper phases; block copolymers; conformational asymmetry; quasicrystals; self-assembly; Frank-Kasper phase; block copolymer; quasicrystal
Citation Formats
Jeon, Seungbae, Jun, Taesuk, Jo, Seongjun, Ahn, Hyungju, Lee, Seungwoo, Lee, Byeongdu, and Ryu, Du Yeol. Frank–Kasper Phases Identified in PDMS-b-PTFEA Copolymers with High Conformational Asymmetry. United States: N. p., 2019.
Web. doi:10.1002/marc.201900259.
Jeon, Seungbae, Jun, Taesuk, Jo, Seongjun, Ahn, Hyungju, Lee, Seungwoo, Lee, Byeongdu, & Ryu, Du Yeol. Frank–Kasper Phases Identified in PDMS-b-PTFEA Copolymers with High Conformational Asymmetry. United States. https://doi.org/10.1002/marc.201900259
Jeon, Seungbae, Jun, Taesuk, Jo, Seongjun, Ahn, Hyungju, Lee, Seungwoo, Lee, Byeongdu, and Ryu, Du Yeol. Wed .
"Frank–Kasper Phases Identified in PDMS-b-PTFEA Copolymers with High Conformational Asymmetry". United States. https://doi.org/10.1002/marc.201900259. https://www.osti.gov/servlets/purl/1574376.
@article{osti_1574376,
title = {Frank–Kasper Phases Identified in PDMS-b-PTFEA Copolymers with High Conformational Asymmetry},
author = {Jeon, Seungbae and Jun, Taesuk and Jo, Seongjun and Ahn, Hyungju and Lee, Seungwoo and Lee, Byeongdu and Ryu, Du Yeol},
abstractNote = {In the search for the formation of Frank–Kasper phases from diblock copolymer self-assembly, a series of compositionally asymmetric poly(dimethylsiloxane)-b-poly(2,2,2-triflouroethyl acrylate)s (PDMS-b-PTFEAs) are synthesized to produce PDMS-rich phases with PDMS volume fractions (ƒPDMS) ranging from 0.746 to 0.869. As determined by small-angle X-ray scattering analysis, the Frank–Kasper σ and C14 phases are identified at ƒPDMS = 0.796 and 0.851, respectively, plausibly due to high conformational asymmetry (ε ≈ 2.20) between the two blocks. Intriguingly, the σ phase develops during heating from a short-range liquid-like packing (LLP) state, whereas the C14 phase is achieved at room temperature, which are both followed by a disordering at higher temperatures. Based on thermal experiments from a super cooled disordered state, the findings further provide compelling evidence of an LLP-hexagonally packed cylinder-σ transition and a direct pathway to the C14 phase during heating from an LLP state.},
doi = {10.1002/marc.201900259},
journal = {Macromolecular Rapid Communications},
number = 19,
volume = 40,
place = {United States},
year = {Wed Jul 10 00:00:00 EDT 2019},
month = {Wed Jul 10 00:00:00 EDT 2019}
}
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Figures / Tables:
Figure 1: Chemical structures, synthetic routes, and molecular schamatics of PDMS-b-PTFEA. A molecular schematic (left) depicts a PDMS-rich PDMS-b-PTFEA copolymer, where the blue and red colors designate the flexible PDMS and rigid PTFEA blocks, respectively. The 3D schematic (right) illustrates a possible polyhedron (with the coordination number of 12) consistingmore »
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Works referencing / citing this record:
Small‐Molecule Modulation of Soft‐Matter Frank–Kasper Phases: A Method for Adding Function to Form
journal, January 2020
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Small‐Molecule Modulation of Soft‐Matter Frank–Kasper Phases: A Method for Adding Function to Form
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