Phase Behavior of Salt-Doped A/B/AB Ternary Polymer Blends: The Role of Homopolymer Distribution

Xie, Shuyi; Zhang, Bo; Bates, Frank S.; Lodge, Timothy P.

doi:10.1021/acs.macromol.1c00928

Title: Phase Behavior of Salt-Doped A/B/AB Ternary Polymer Blends: The Role of Homopolymer Distribution

Abstract

Salt-doped A/B/AB ternary polymer blends demonstrate a plethora of nanostructured morphologies tunable by the composition of homopolymers (A and B) and the corresponding diblock copolymer (AB). Here we report a complete phase diagram of lithium bis(trifluoromethane) sulfonimide (LiTFSI)-doped low-molar-mass polystyrene (PS)/ poly(ethylene oxide) (PEO)/symmetric PS-b-PEO block copolymer (SO) blends, and evaluate the spatial distribution of homopolymers in the resulting microstructures. In the isothermal phase triangle at 120 °C and r = [Li⁺]/[EO] = 0.06, a wide region of lamellae (LAM) is bracketed by small zones of double gyroid (GYR) and wide regions of hexagonally packed cylinders (HEX); adjacent to HEX is a significant region of the C15 Laves phase. At a high total homopolymer composition Φ_H = Φ_PS,homo + Φ_{PEO,homo+LiTFSI}, the copolymer brush becomes saturated and begins to exclude homopolymers, resulting in a rapid domain size increase and inducing the formation of higher curvature phases, as suggested by small-angle X-ray scattering (SAXS). This phenomenon is distinct from charge-neutral ternary blends. Moreover, small-angle neutron scattering (SANS) profiles of selectively deuterated lamellar and bicontinuous ternary blends with contrast variation confirm the existence of a pure PS homopolymer layer in the middle of the PS microdomain.

Authors:

;

Publication Date:: Fri Jul 16 00:00:00 EDT 2021

Research Org.:: Univ. of Minnesota, Twin Cities, MN (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1859567

Alternate Identifier(s):: OSTI ID: 1831776

Grant/Contract Number:: FOA-0001664; SC0017809; AC02-06CH11357

Resource Type:: Published Article

Journal Name:: Macromolecules

Additional Journal Information:: Journal Name: Macromolecules Journal Volume: 54 Journal Issue: 14; Journal ID: ISSN 0024-9297

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; Interfaces; Copolymers; Scattering; Homopolymers; Phase transitions

Citation Formats


                    Xie, Shuyi, Zhang, Bo, Bates, Frank S., and Lodge, Timothy P. Phase Behavior of Salt-Doped A/B/AB Ternary Polymer Blends: The Role of Homopolymer Distribution.  United States: N. p., 2021. 
Web.  doi:10.1021/acs.macromol.1c00928.

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                    Xie, Shuyi, Zhang, Bo, Bates, Frank S., & Lodge, Timothy P. Phase Behavior of Salt-Doped A/B/AB Ternary Polymer Blends: The Role of Homopolymer Distribution.  United States.  https://doi.org/10.1021/acs.macromol.1c00928

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                    Xie, Shuyi, Zhang, Bo, Bates, Frank S., and Lodge, Timothy P. Fri .  
"Phase Behavior of Salt-Doped A/B/AB Ternary Polymer Blends: The Role of Homopolymer Distribution".  United States.  https://doi.org/10.1021/acs.macromol.1c00928.

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@article{osti_1859567,

  title        = {Phase Behavior of Salt-Doped A/B/AB Ternary Polymer Blends: The Role of Homopolymer Distribution},

  author       = {Xie, Shuyi and Zhang, Bo and Bates, Frank S. and Lodge, Timothy P.},

  abstractNote = {Salt-doped A/B/AB ternary polymer blends demonstrate a plethora of nanostructured morphologies tunable by the composition of homopolymers (A and B) and the corresponding diblock copolymer (AB). Here we report a complete phase diagram of lithium bis(trifluoromethane) sulfonimide (LiTFSI)-doped low-molar-mass polystyrene (PS)/ poly(ethylene oxide) (PEO)/symmetric PS-b-PEO block copolymer (SO) blends, and evaluate the spatial distribution of homopolymers in the resulting microstructures. In the isothermal phase triangle at 120 °C and r = [Li+]/[EO] = 0.06, a wide region of lamellae (LAM) is bracketed by small zones of double gyroid (GYR) and wide regions of hexagonally packed cylinders (HEX); adjacent to HEX is a significant region of the C15 Laves phase. At a high total homopolymer composition ΦH = ΦPS,homo + ΦPEO,homo+LiTFSI, the copolymer brush becomes saturated and begins to exclude homopolymers, resulting in a rapid domain size increase and inducing the formation of higher curvature phases, as suggested by small-angle X-ray scattering (SAXS). This phenomenon is distinct from charge-neutral ternary blends. Moreover, small-angle neutron scattering (SANS) profiles of selectively deuterated lamellar and bicontinuous ternary blends with contrast variation confirm the existence of a pure PS homopolymer layer in the middle of the PS microdomain.},

  doi          = {10.1021/acs.macromol.1c00928},

  journal      = {Macromolecules},

  number       = 14,

  volume       = 54,

  place        = {United States},

  year         = {Fri Jul 16 00:00:00 EDT 2021},

  month        = {Fri Jul 16 00:00:00 EDT 2021}

}

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Title: Phase Behavior of Salt-Doped A/B/AB Ternary Polymer Blends: The Role of Homopolymer Distribution

Abstract

Citation Formats

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Origin of the scattering peak in microemulsions journal, September 1987

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Formation of a C15 Laves Phase with a Giant Unit Cell in Salt-Doped A/B/AB Ternary Polymer Blends journal, August 2020

Fluctuation Effects in Ternary AB + A + B Polymeric Emulsions journal, December 2003

Model Bicontinuous Microemulsions in Ternary Homopolymer/Block Copolymer Blends journal, June 1999

Comparing Experimental Phase Behavior of Ion-Doped Block Copolymers with Theoretical Predictions Based on Selective Ion Solvation journal, May 2020

Structure and Properties of Bicontinuous Microemulsions from Salt-Doped Ternary Polymer Blends journal, December 2019

Phase Behavior of Ternary Homopolymer/Diblock Blends: Influence of Relative Chain Lengths journal, January 1997

Influence of Conformational Asymmetry on the Phase Behavior of Ternary Homopolymer/Block Copolymer Blends around the Bicontinuous Microemulsion Channel journal, March 2006

Influence of Conformational Asymmetry on Polymer−Polymer Interactions: An Entropic or Enthalpic Effect?
journal, September 2002

Local geometry of surfactant monolayers in a ternary microemulsion system
journal, July 1994

A Record Nine Different Phases (Four Cubic, Two Hexagonal, and One Lamellar Lyotropic Liquid Crystalline and Two Micellar Solutions) in a Ternary Isothermal System of an Amphiphilic Block Copolymer and Selective Solvents (Water and Oil)
journal, May 1998

Ordered structure in mixtures of a block copolymer and homopolymers. 2. Effects of molecular weights of homopolymers
journal, October 1990

Polymeric Bicontinuous Microemulsions
journal, August 1997

Origin of the scattering peak in microemulsions
journal, September 1987

Conformationally asymmetric block copolymers
journal, April 1997

Swelling of Copolymer Micelles by Added Homopolymer
journal, August 1994

Connection between Polymer Molecular Weight, Density, Chain Dimensions, and Melt Viscoelastic Properties
journal, August 1994

Coexistence of Polymeric Microemulsion with Homopolymer-Rich Phases
journal, January 2021

Ordered Structure in Blends of Block Copolymers. 5. Blends of Lamella-Forming Block Copolymers Showing both Microphase Separation Involving Unique Morphological Transitions and Macrophase Separation ^†
journal, October 2000

Ordered structure in mixtures of a block copolymer and homopolymers. 1. Solubilization of low molecular weight homopolymers
journal, January 1991

Investigating the Effect of Added Salt on the Chain Dimensions of Poly(ethylene oxide) through Small-Angle Neutron Scattering
journal, November 2019

Monte Carlo Simulations of the Phase Behavior of Surfactant Solutions
journal, October 1996

Conformational Asymmetry and Polymer-Polymer Thermodynamics
journal, July 1994

Influence of Added Salt on Chain Conformations in Poly(ethylene oxide) Melts: SANS Analysis with Complications
journal, August 2020

Phase Behavior of Diblock Copolymer–Homopolymer Ternary Blends with a Compositionally Asymmetric Diblock Copolymer
journal, December 2020

Effects of Ion Solvation on the Miscibility of Binary Polymer Blends ^†
journal, December 2008

Swelling of lamellar diblock copolymer by homopolymer: influences of homopolymer concentration and molecular weight
journal, November 1991

Ordered Network Phases in Linear Poly(isoprene- b -styrene- b -ethylene oxide) Triblock Copolymers
journal, November 2004

Ordered structures of block polymer/homopolymer mixtures. 3. Temperature dependence
journal, September 1991

Phase Behavior of Mixtures of Block Copolymers and a Lithium Salt
journal, August 2018

Thermodynamic and Structural Changes in Ion-Containing Symmetric Diblock Copolymers: A Small-Angle X-ray Scattering Study
journal, December 2011

Phase equilibria in copolymer/homopolymer ternary blends: Molecular weight effects
journal, August 1990

Scattering from internal interfaces in microemulsion and sponge phases
journal, February 1994

Ordered morphologies in binary blends of diblock copolymer and homopolymer and characterization of their intermaterial dividing surfaces
journal, December 1991

Thermodynamic Properties of Block Copolymer Electrolytes Containing Imidazolium and Lithium Salts
journal, October 2010

Phase Behavior of Block Copolymer/Homopolymer Blends
journal, August 1995

Spatial Distribution of Homopolymers in Block Copolymer Microdomains As Observed by a Combined SANS and SAXS Method
journal, December 1994

Diverse Morphologies of Block Copolymers by Blending with Homo (and Co) Polymers
journal, June 2020

Bicontinuous Microemulsions in Partially Charged Ternary Polymer Blends
journal, August 2019

Composition Dependence of the Flory–Huggins Interaction Parameters of Block Copolymer Electrolytes and the Isotaksis Point
journal, July 2019

Instability of the Microemulsion Channel in Block Copolymer-Homopolymer Blends
journal, September 2020

Organizing thermodynamic data obtained from multicomponent polymer electrolytes: Salt‐containing polymer blends and block copolymers
journal, February 2019

Effects of Segment Length Asymmetry in Ternary Diblock Co-polymer–Homopolymer Mixtures
journal, May 2019

Effect of Ion Concentration on the Formation of Bicontinuous Microemulsions in Partially Charged Ternary Polymer Blends
journal, December 2019

Ternary Polymer Blends as Model Surfactant Systems
journal, August 2000

Reduction and analysis of SANS and USANS data using IGOR Pro
journal, November 2006

Thermal composition fluctuations near the isotropic Lifshitz critical point in a ternary mixture of a homopolymer blend and diblock copolymer
journal, March 2000

Ordered structure of block polymer/homopolymer mixtures, 4. Vesicle formation and macrophase separation
journal, September 1992

Small-angle neutron scattering from diffuse interfaces. 1. Mono- and bilayers in the water-octane-pentaoxyethylene monododecyl ether (C12Es) system
journal, September 1991

Phase Behavior of Diblock Copolymer–Homopolymer Ternary Blends: Congruent First-Order Lamellar–Disorder Transition
journal, October 2016

Phase Behavior of Binary Polymer Blends Doped with Salt
journal, December 2017

Effects of Ion-Induced Cross-Linking on the Phase Behavior in Salt-Doped Polymer Blends
journal, December 2015

Formation of a C15 Laves Phase with a Giant Unit Cell in Salt-Doped A/B/AB Ternary Polymer Blends
journal, August 2020

Fluctuation Effects in Ternary AB + A + B Polymeric Emulsions
journal, December 2003

Model Bicontinuous Microemulsions in Ternary Homopolymer/Block Copolymer Blends
journal, June 1999

Comparing Experimental Phase Behavior of Ion-Doped Block Copolymers with Theoretical Predictions Based on Selective Ion Solvation
journal, May 2020

Structure and Properties of Bicontinuous Microemulsions from Salt-Doped Ternary Polymer Blends
journal, December 2019

Phase Behavior of Ternary Homopolymer/Diblock Blends: Influence of Relative Chain Lengths
journal, January 1997

Influence of Conformational Asymmetry on the Phase Behavior of Ternary Homopolymer/Block Copolymer Blends around the Bicontinuous Microemulsion Channel
journal, March 2006