Tuning Diblock Copolymer Particle Packing Symmetry with Variable Molecular Weight Core-Homopolymers

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

doi:10.1021/acs.macromol.2c01267

Tuning Diblock Copolymer Particle Packing Symmetry with Variable Molecular Weight Core-Homopolymers

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

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

13 Scopus citations

Abstract

We report the sensitivity of diblock copolymer particle packing symmetry to the ratio α = N_homo/N_core, where N_homoand N_coreare the respective homopolymer and core-block degrees of polymerization. Three poly(ethylene oxide)-b-poly(2-ethylhexyl acrylate) (OA) diblock copolymers with O volume fractions f_O= 0.15, 0.16, and 0.20 were blended with O homopolymers characterized by α = 0.23, 0.42, 0.80, and 1.00. Small-angle X-ray scattering revealed rich phase behavior as a function of α, the overall particle core volume fraction (f_core), and temperature. BCC, HCP, and Frank-Kasper σ, C14, C15, and dodecagonal quasicrystal phases, were all identified. "Dry-brush" homopolymer distribution (α = 0.80 and 1.00) favor C14 and C15 phases with macrophase separation at high homopolymer loadings. "Wet-brush" homopolymer distributions in the particle cores (α = 0.42) lead to narrow σ or C15 windows and cylinders at greater O concentrations. Solvent-like swelling (α = 0.23) favors widespread σ phase formation.

Original language	English (US)
Pages (from-to)	8332-8344
Number of pages	13
Journal	Macromolecules
Volume	55
Issue number	18
DOIs	https://doi.org/10.1021/acs.macromol.2c01267
State	Published - Sep 27 2022

Bibliographical note

Funding Information:
Financial support for this work was provided by the U.S. National Science Foundation under grants DMR-1801993 (A.J.M., F.S.B.) and CHE-1807330 (A.J., M.K.M.), and through an NSF Graduate Research Fellowship under Grant No. 00039202 (A.P.L.). SAXS experiments were carried out at Sector 12 and Sector 5 of the Advanced Photon Source (APS). The Sector 5 DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) is supported by E.I. DuPont de Nemours & Co., the Dow Chemical Company, and Northwestern University. Use of the APS, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under Contract No. DE-AC02-06CH11357. Parts of this work, including lab source SAXS analyses, were carried out in the Characterization Facility at the University of Minnesota, which receives partial support from NSF through the UMN MRSEC (DMR-2011401). H NMR spectra used in this study were collected on a Bruker Avance II HD 400 MHz spectrometer purchased by the Office of the Vice President of Research, the College of Science of and Engineering, and the Department of Chemistry at the University of Minnesota. MALDI-ToF data were obtained at the Mass Spectroscopy Laboratory located in the Chemistry Department at the University of Minnesota, supported by the Office of the Vice President of Research, the College of Science and Engineering, and the Department of Chemistry at the University of Minnesota, as well as the National Science Foundation (NSF CHE-1336940). 1

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title = "Tuning Diblock Copolymer Particle Packing Symmetry with Variable Molecular Weight Core-Homopolymers",

abstract = "We report the sensitivity of diblock copolymer particle packing symmetry to the ratio α = Nhomo/Ncore, where Nhomoand Ncoreare the respective homopolymer and core-block degrees of polymerization. Three poly(ethylene oxide)-b-poly(2-ethylhexyl acrylate) (OA) diblock copolymers with O volume fractions fO= 0.15, 0.16, and 0.20 were blended with O homopolymers characterized by α = 0.23, 0.42, 0.80, and 1.00. Small-angle X-ray scattering revealed rich phase behavior as a function of α, the overall particle core volume fraction (fcore), and temperature. BCC, HCP, and Frank-Kasper σ, C14, C15, and dodecagonal quasicrystal phases, were all identified. {"}Dry-brush{"} homopolymer distribution (α = 0.80 and 1.00) favor C14 and C15 phases with macrophase separation at high homopolymer loadings. {"}Wet-brush{"} homopolymer distributions in the particle cores (α = 0.42) lead to narrow σ or C15 windows and cylinders at greater O concentrations. Solvent-like swelling (α = 0.23) favors widespread σ phase formation.",

author = "Mueller, {Andreas J} and Lindsay, {Aaron P.} and Ashish Jayaraman and Steven Weigand and Lodge, {Timothy P.} and Mahanthappa, {Mahesh K.} and Bates, {Frank S}",

note = "Funding Information: Financial support for this work was provided by the U.S. National Science Foundation under grants DMR-1801993 (A.J.M., F.S.B.) and CHE-1807330 (A.J., M.K.M.), and through an NSF Graduate Research Fellowship under Grant No. 00039202 (A.P.L.). SAXS experiments were carried out at Sector 12 and Sector 5 of the Advanced Photon Source (APS). The Sector 5 DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) is supported by E.I. DuPont de Nemours & Co., the Dow Chemical Company, and Northwestern University. Use of the APS, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under Contract No. DE-AC02-06CH11357. Parts of this work, including lab source SAXS analyses, were carried out in the Characterization Facility at the University of Minnesota, which receives partial support from NSF through the UMN MRSEC (DMR-2011401). H NMR spectra used in this study were collected on a Bruker Avance II HD 400 MHz spectrometer purchased by the Office of the Vice President of Research, the College of Science of and Engineering, and the Department of Chemistry at the University of Minnesota. MALDI-ToF data were obtained at the Mass Spectroscopy Laboratory located in the Chemistry Department at the University of Minnesota, supported by the Office of the Vice President of Research, the College of Science and Engineering, and the Department of Chemistry at the University of Minnesota, as well as the National Science Foundation (NSF CHE-1336940). 1 Publisher Copyright: {\textcopyright} 2022 American Chemical Society. All rights reserved.",

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AU - Mueller, Andreas J

AU - Lindsay, Aaron P.

AU - Jayaraman, Ashish

AU - Weigand, Steven

AU - Lodge, Timothy P.

AU - Mahanthappa, Mahesh K.

AU - Bates, Frank S

N1 - Funding Information: Financial support for this work was provided by the U.S. National Science Foundation under grants DMR-1801993 (A.J.M., F.S.B.) and CHE-1807330 (A.J., M.K.M.), and through an NSF Graduate Research Fellowship under Grant No. 00039202 (A.P.L.). SAXS experiments were carried out at Sector 12 and Sector 5 of the Advanced Photon Source (APS). The Sector 5 DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) is supported by E.I. DuPont de Nemours & Co., the Dow Chemical Company, and Northwestern University. Use of the APS, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under Contract No. DE-AC02-06CH11357. Parts of this work, including lab source SAXS analyses, were carried out in the Characterization Facility at the University of Minnesota, which receives partial support from NSF through the UMN MRSEC (DMR-2011401). H NMR spectra used in this study were collected on a Bruker Avance II HD 400 MHz spectrometer purchased by the Office of the Vice President of Research, the College of Science of and Engineering, and the Department of Chemistry at the University of Minnesota. MALDI-ToF data were obtained at the Mass Spectroscopy Laboratory located in the Chemistry Department at the University of Minnesota, supported by the Office of the Vice President of Research, the College of Science and Engineering, and the Department of Chemistry at the University of Minnesota, as well as the National Science Foundation (NSF CHE-1336940). 1 Publisher Copyright: © 2022 American Chemical Society. All rights reserved.

PY - 2022/9/27

Y1 - 2022/9/27

N2 - We report the sensitivity of diblock copolymer particle packing symmetry to the ratio α = Nhomo/Ncore, where Nhomoand Ncoreare the respective homopolymer and core-block degrees of polymerization. Three poly(ethylene oxide)-b-poly(2-ethylhexyl acrylate) (OA) diblock copolymers with O volume fractions fO= 0.15, 0.16, and 0.20 were blended with O homopolymers characterized by α = 0.23, 0.42, 0.80, and 1.00. Small-angle X-ray scattering revealed rich phase behavior as a function of α, the overall particle core volume fraction (fcore), and temperature. BCC, HCP, and Frank-Kasper σ, C14, C15, and dodecagonal quasicrystal phases, were all identified. "Dry-brush" homopolymer distribution (α = 0.80 and 1.00) favor C14 and C15 phases with macrophase separation at high homopolymer loadings. "Wet-brush" homopolymer distributions in the particle cores (α = 0.42) lead to narrow σ or C15 windows and cylinders at greater O concentrations. Solvent-like swelling (α = 0.23) favors widespread σ phase formation.

AB - We report the sensitivity of diblock copolymer particle packing symmetry to the ratio α = Nhomo/Ncore, where Nhomoand Ncoreare the respective homopolymer and core-block degrees of polymerization. Three poly(ethylene oxide)-b-poly(2-ethylhexyl acrylate) (OA) diblock copolymers with O volume fractions fO= 0.15, 0.16, and 0.20 were blended with O homopolymers characterized by α = 0.23, 0.42, 0.80, and 1.00. Small-angle X-ray scattering revealed rich phase behavior as a function of α, the overall particle core volume fraction (fcore), and temperature. BCC, HCP, and Frank-Kasper σ, C14, C15, and dodecagonal quasicrystal phases, were all identified. "Dry-brush" homopolymer distribution (α = 0.80 and 1.00) favor C14 and C15 phases with macrophase separation at high homopolymer loadings. "Wet-brush" homopolymer distributions in the particle cores (α = 0.42) lead to narrow σ or C15 windows and cylinders at greater O concentrations. Solvent-like swelling (α = 0.23) favors widespread σ phase formation.

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Tuning Diblock Copolymer Particle Packing Symmetry with Variable Molecular Weight Core-Homopolymers

Abstract

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Tuning Diblock Copolymer Particle Packing Symmetry with Variable Molecular Weight Core-Homopolymers

Abstract

Bibliographical note

MRSEC Support

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University of Minnesota Materials Research Science and Engineering Center (DMR-2011401)

IRG-2: Mesoscale Network Materials

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