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Title: Phase Behavior of Diblock Copolymer–Homopolymer Ternary Blends: Congruent First-Order Lamellar–Disorder Transition

Abstract

We have established the existence of a line of congruent first-order lamellar-to-disorder (LAM–DIS) transitions when appropriate amounts of poly(cyclohexylethylene) (C) and poly(ethylene) (E) homopolymers are mixed with a corresponding compositionally symmetric CE diblock copolymer. The line of congruent transitions, or the congruent isopleth, terminates at the bicontinuous microemulsion (BμE) channel, and its trajectory appears to be influenced by the critical composition of the C/E binary homopolymer blend. Blends satisfying congruency undergo a direct LAM–DIS transition without passing through a two-phase region. We present complementary optical transmission, small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), and dynamic mechanical spectroscopy (DMS) results that establish the phase behavior at constant copolymer volume fraction and varying C/E homopolymer volume ratios. Adjacent to the congruent composition at constant copolymer volume fraction, the lamellar and disordered phases are separated by two-phase coexistence windows, which converge, along with the line of congruent transitions, at an overall composition in the phase prism coincident with the BμE channel. Hexagonal and cubic (double gyroid) phases occur at higher diblock copolymer concentrations for asymmetric amounts of C and E homopolymers. These results establish a quantitative method for identifying the detailed phase behavior of ternary diblock copolymer–homopolymer blends, especially in the vicinitymore » of the BμE.« less

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE
OSTI Identifier:
1335977
Resource Type:
Journal Article
Resource Relation:
Journal Name: Macromolecules; Journal Volume: 49; Journal Issue: 20
Country of Publication:
United States
Language:
ENGLISH
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Hickey, Robert J., Gillard, Timothy M., Irwin, Matthew T., Morse, David C., Lodge, Timothy P., and Bates, Frank S. Phase Behavior of Diblock Copolymer–Homopolymer Ternary Blends: Congruent First-Order Lamellar–Disorder Transition. United States: N. p., 2016. Web. doi:10.1021/acs.macromol.6b01872.
Hickey, Robert J., Gillard, Timothy M., Irwin, Matthew T., Morse, David C., Lodge, Timothy P., & Bates, Frank S. Phase Behavior of Diblock Copolymer–Homopolymer Ternary Blends: Congruent First-Order Lamellar–Disorder Transition. United States. doi:10.1021/acs.macromol.6b01872.
Hickey, Robert J., Gillard, Timothy M., Irwin, Matthew T., Morse, David C., Lodge, Timothy P., and Bates, Frank S. Thu . "Phase Behavior of Diblock Copolymer–Homopolymer Ternary Blends: Congruent First-Order Lamellar–Disorder Transition". United States. doi:10.1021/acs.macromol.6b01872.
@article{osti_1335977,
title = {Phase Behavior of Diblock Copolymer–Homopolymer Ternary Blends: Congruent First-Order Lamellar–Disorder Transition},
author = {Hickey, Robert J. and Gillard, Timothy M. and Irwin, Matthew T. and Morse, David C. and Lodge, Timothy P. and Bates, Frank S.},
abstractNote = {We have established the existence of a line of congruent first-order lamellar-to-disorder (LAM–DIS) transitions when appropriate amounts of poly(cyclohexylethylene) (C) and poly(ethylene) (E) homopolymers are mixed with a corresponding compositionally symmetric CE diblock copolymer. The line of congruent transitions, or the congruent isopleth, terminates at the bicontinuous microemulsion (BμE) channel, and its trajectory appears to be influenced by the critical composition of the C/E binary homopolymer blend. Blends satisfying congruency undergo a direct LAM–DIS transition without passing through a two-phase region. We present complementary optical transmission, small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), and dynamic mechanical spectroscopy (DMS) results that establish the phase behavior at constant copolymer volume fraction and varying C/E homopolymer volume ratios. Adjacent to the congruent composition at constant copolymer volume fraction, the lamellar and disordered phases are separated by two-phase coexistence windows, which converge, along with the line of congruent transitions, at an overall composition in the phase prism coincident with the BμE channel. Hexagonal and cubic (double gyroid) phases occur at higher diblock copolymer concentrations for asymmetric amounts of C and E homopolymers. These results establish a quantitative method for identifying the detailed phase behavior of ternary diblock copolymer–homopolymer blends, especially in the vicinity of the BμE.},
doi = {10.1021/acs.macromol.6b01872},
journal = {Macromolecules},
number = 20,
volume = 49,
place = {United States},
year = {Thu Oct 13 00:00:00 EDT 2016},
month = {Thu Oct 13 00:00:00 EDT 2016}
}