Various Low-Symmetry Phases in High-χ and Conformationally Asymmetric PDMS-b-PTFEA Copolymers

Jeon, Seungbae; Jun, Taesuk; Jeon, Hui Il; Ahn, Hyungju; Lee, Sangwoo; Lee, Byeongdu; Ryu, Du Yeol

doi:10.1021/acs.macromol.1c01760

Title: Various Low-Symmetry Phases in High-χ and Conformationally Asymmetric PDMS-b-PTFEA Copolymers

Journal Article · Mon Oct 04 00:00:00 EDT 2021 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.1c01760· OSTI ID:1897895

Jeon, Seungbae ^[1]; Jun, Taesuk ^[1]; Jeon, Hui Il ^[1]; Ahn, Hyungju ^[2];

^[3];

^[4];

^[1]

Yonsei Univ., Seoul (Korea, Republic of)
Pohang Accelerator Lab. (PAL) (Korea, Republic of)
Rensselaer Polytechnic Inst., Troy, NY (United States)
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Since the discovery of the Frank–Kasper (FK) phase a decade ago, single-component block copolymer systems have offered unique opportunities to explore the structural and phase-transition properties of topologically close-packed FK phases composed of point-particle motifs. Here, we present the formation of complex low-symmetry phases and their thermodynamic stability using high-χ and high-ε linear diblock copolymers, where χ and ε are the Flory–Huggins interaction parameter and conformational asymmetry between the two blocks, respectively. In this work, a series of polydimethylsiloxane-b-poly(2,2,2-trifluoroethyl acrylate) (PDMS-b-PTFEA) copolymers are prepared by tuning the volume fraction ($$f_{\text{PTFEA}}$$) of a minor PTFEA block. The packing structures of PDMS-b-PTFEAs are mapped in the space of temperature versus $$f_{\text{PTFEA}}$$ using X-ray scattering measurements. In addition to the packing structures reported earlier, we identify another A15 phase at higher $$f_{\text{PTFEA}}$$ close to a hexagonally packed cylinder (HEX) phase and establish the phase sequence of HEX–A15–σ–C14–BCC with decreasing $$f_{\text{PTFEA}}$$. Theoretical calculation of relative free-energy densities confirms the experimental phase sequence of the composition-dependent sphere-packing structures. Interestingly, the domain sizes of three-dimensional (3D) sphere-packing structures are nearly temperature-invariant compared to that of a two-dimensional HEX structure, and we attribute this dimensional stability to the strong enthalpic effects in the formation of 3D packing structures and the geometrical characteristics of spherical domains. Our results demonstrate that the interaction parameter χ, together with the known role of conformational asymmetry ε, serves as the primary thermodynamic parameter for selecting and stabilizing various low-symmetry packing structures in sphere-forming linear diblock copolymer systems.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: Samsung Electronics; USDOE Office of Science (SC), Basic Energy Sciences (BES); National Research Foundation of Korea (NRF); Ministry of Science, ICT & Future Planning (MSIP)

Grant/Contract Number:: AC02-06CH11357; 2021R1A2C2006588

OSTI ID:: 1897895

Journal Information:: Macromolecules, Vol. 54, Issue 20; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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