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Title: Extreme Deflection of Phase Boundaries and Chain Bridging in A(BA')n Miktoarm Star Polymers

Journal Article · · Macromolecules

In this study, we use self-consistent field theory to demonstrate that the A(BA')n miktoarm architecture can strongly deflect order–order phase boundaries to large volume fractions fA. The A(BA')n architecture achieves this strong deflection by combining the effects of miktoarm frustration and block bidispersity and is shown to stabilize discrete spheres and cylinders of the A block up to values of $$f_A$$ = 0.58 and $$f_A$$ = 0.78, respectively. Next, we analyze the prevalence of chain bridging $$ν_B$$ in both neat miktoarm melts and in homopolymer blends that form the fluctuation-stabilized “bricks and mortar” phase. These calculations demonstrate that high $$ν_B$$ and $$f_A$$ can both be simultaneously achieved with highly asymmetric miktoarm stars, a property especially useful for the design of tough thermoplastic elastomers. Lastly, we show that these miktoarms exhibit large windows of phase space where the σ and A15 Frank–Kasper phases are stable.

Research Organization:
Univ. of California, Santa Barbara, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Grant/Contract Number:
SC0019001; CNS-1725797; DMR-1720256
OSTI ID:
1594760
Journal Information:
Macromolecules, Vol. 53, Issue 2; ISSN 0024-9297
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 29 works
Citation information provided by
Web of Science

References (43)

Block Copolymer Thermodynamics: Theory and Experiment journal October 1990
Block Copolymers—Designer Soft Materials journal February 1999
Theory of Microphase Separation in Block Copolymers journal November 1980
Stable and unstable phases of a diblock copolymer melt journal April 1994
Existence of fcc-Packed Spherical Micelles in Diblock Copolymer Melt journal February 2007
Effect of Architecture on the Phase Behavior of AB-Type Block Copolymer Melts journal February 2012
Morphology and miscibility of miktoarm styrene-diene copolymers and terpolymers journal October 1993
Morphologies of Microphase-Separated A 2 B Simple Graft Copolymers journal January 1996
Chain Architecture and Asymmetry in Copolymer Microphases journal April 1994
Interfaces in Diblocks:  A Study of Miktoarm Star Copolymers journal September 2004
I 5 S Miktoarm Star Block Copolymers:  Packing Constraints on Morphology and Discontinuous Chevron Tilt Grain Boundaries journal December 2001
σ Phase Formed in Conformationally Asymmetric AB-Type Block Copolymers journal August 2014
Conformational Asymmetry and Quasicrystal Approximants in Linear Diblock Copolymers journal May 2017
Stability of the A15 phase in diblock copolymer melts journal June 2019
Bending moduli of polymeric surfactant interfaces journal January 1988
Effects of polydispersity in the end-grafted polymer brush journal March 1989
Equilibrium behavior of asymmetric ABA triblock copolymer melts journal January 2000
Theory of Polydisperse Inhomogeneous Polymers journal July 2003
Continuous polydispersity in a self-consistent field theory for diblock copolymers journal September 2004
Effects of Polydispersity on Phase Behavior of Diblock Copolymers journal September 2006
Influence of Polydispersity on the Self-Assembly of Diblock Copolymers journal October 2005
Effects of Polydispersity on the Order−Disorder Transition in Block Copolymer Melts journal October 2007
Unexpected Consequences of Block Polydispersity on the Self-Assembly of ABA Triblock Copolymers journal February 2012
Equilibrium behavior of symmetric ABA triblock copolymer melts journal October 1999
Design of Soft and Strong Thermoplastic Elastomers Based on Nonlinear Block Copolymer Architectures Using Self-Consistent-Field Theory journal April 2010
Toward Strong Thermoplastic Elastomers with Asymmetric Miktoarm Block Copolymer Architectures journal March 2014
Creating Extremely Asymmetric Lamellar Structures via Fluctuation-Assisted Unbinding of Miktoarm Star Block Copolymer Alloys journal May 2015
Aperiodic “Bricks and Mortar” Mesophase: a New Equilibrium State of Soft Matter and Application as a Stiff Thermoplastic Elastomer journal July 2015
Field-Theoretic Simulations of Fluctuation-Stabilized Aperiodic “Bricks-and-Mortar” Mesophase in Miktoarm Star Block Copolymer/Homopolymer Blends journal August 2017
Efficient Synthesis of Asymmetric Miktoarm Star Polymers journal January 2020
Microphase separation in multiblock copolymer melts journal December 1989
Numerical Solution of Polymer Self-Consistent Field Theory journal January 2004
Improved numerical algorithm for exploring block copolymer mesophases journal July 2002
Recent Developments in Fully Fluctuating Field-Theoretic Simulations of Polymer Melts and Solutions journal July 2016
A multi-species exchange model for fully fluctuating polymer field theory simulations journal November 2014
Optimizing Chain Bridging in Complex Block Copolymers journal July 2001
Domain Bridging in Thermoplastic Elastomers of Star Block Copolymer journal February 2017
Synthesis of model nonlinear block copolymers of A(BA)2, A(BA)3, and (AB)3A(BA)3 type journal March 1997
Miktoarm Stars via Grafting-Through Copolymerization: Self-Assembly and the Star-to-Bottlebrush Transition journal February 2019
Ordered Nanoporous Polymers from Polystyrene−Polylactide Block Copolymers journal October 2002
Nanoporous Materials with Spherical and Gyroid Cavities Created by Quantitative Etching of Polydimethylsiloxane in Polystyrene−Polydimethylsiloxane Block Copolymers journal November 2003
Ultrafiltration by gyroid nanoporous polymer membranes journal November 2011
Solid-State Polymer Electrolytes Based on AB 3 -Type Miktoarm Star Copolymers journal August 2018

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Nonclassical Block Copolymer Self‐Assembly Resulting from a Constrained Location of Chains and Junctions journal February 2020

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