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

Robert J. Hickey, Timothy M. Gillard, Matthew T. Irwin, David C. Morse, Timothy P. Lodge, Frank S. Bates

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23 Scopus citations


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.

Original languageEnglish (US)
Pages (from-to)7928-7944
Number of pages17
Issue number20
StatePublished - Oct 25 2016

Bibliographical note

Funding Information:
This research was supported by the National Science Foundation under Awards DMR-1104368 (F.S.B.) and DMR-01206459 (T.P.L.). Portions of this work were performed at both Sector 12-ID-B and the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source (APS). DND-CAT is supported by E.I. DuPont de Nemours and 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 DE-AC02-06CH11357. Parts of this work were carried out in the Characterization Facility, University of Minnesota, which receives partial support from NSF through the MRSEC program.

Publisher Copyright:
© 2016 American Chemical Society.

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