Self-Assembly of Partially Charged Diblock Copolymer-Homopolymer Ternary Blends

Caini Zheng, Bo Zhang, Frank S Bates, Timothy P. Lodge

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8 Scopus citations


Ternary blends comprising a diblock copolymer and the corresponding homopolymers provide ready access to a variety of morphologies, but the impact of charge on their phase behavior has not been studied extensively. Here, three partially charged ternary blends consisting of symmetric poly[(oligo(ethylene glycol) methyl ether methacrylate-co-oligo(ethylene glycol) propyl sodium sulfonate methacrylate)] (POEGMA#), polystyrene (PS), and POEGMA#-PS with different charge fractions were prepared, where # denotes the mole fraction of charged monomers in the POEGMA chain. The phase behavior was systematically studied using small-angle X-ray scattering, and isothermal phase diagrams at 120 °C were constructed. The resulting isothermal planes contain a wide lamellar phase window with a slight deviation from symmetry for ion-containing ternary blends due to the homopolymer size difference. Given the absence of any significant change in the phase diagrams as the charge fraction increases, the role of charge is primarily to increase the segregation strength in the ternary system, as in the case of partially charged diblock polymers. In addition, examination of the increase in domain size along the volumetrically symmetric isopleth reveals a "dry-brush"-like swelling behavior of homopolymers in all three blends, presumably due to the space-filling nature of the oligomeric ethylene glycol side chains on POEGMA.

Original languageEnglish (US)
Pages (from-to)4766-4775
Number of pages10
Issue number11
StatePublished - Jun 14 2022

Bibliographical note

Funding Information:
The work was supported by grant DE-SC0017809 funded by the U.S. Department of Energy (DOE), Office of Science. SAXS experiments were carried out in sector 5 (DuPont-Northwestern-Dow Collaborative Access Team, DND-CAT) and sector 12 of the Advanced Photon Source (APS). DND-CAT is supported by Northwestern University, the Dow Chemical Company, and DuPont de Nemours, Inc. This research used resources of the Advanced Photon Source, a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by the Argonne National Laboratory under contract no. DE-AC02-06CH11357. Parts of this work were carried out in the Characterization Facility, University of Minnesota, which receives partial support from the NSF through the MRSEC (award number DMR-2011401) and the NNCI (award number ECCS-2025124) programs.

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© 2022 American Chemical Society.

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