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Controlling the self-assembly of binary copolymer mixtures in solution through molecular architecture

McLeish, Tom C B; Butler, Michael F.; Buzza, D. Martin A; Atkins, Derek; Furzeland, Steve; Schuetz, Peter; Greenall, Martin J.


Tom C B McLeish

Michael F. Butler

Derek Atkins

Steve Furzeland

Peter Schuetz

Martin J. Greenall


We present a combined experimental and theoretical study on the role of copolymer architecture in the self-assembly of binary PEO-PCL mixtures in water-THF and show that altering the chain geometry and composition of the copolymers can control the form of the self-assembled structures and lead to the formation of novel aggregates. First, using transmission electron microscopy and turbidity measurements, we study a mixture of sphere-forming and lamella-forming PEO-PCL copolymers and show that increasing the molecular weight of the lamella-former at a constant ratio of its hydrophilic and hydrophobic components leads to the formation of highly curved structures even at low sphere-former concentrations. This result is explained using a simple argument based on the effective volumes of the two sections of the diblock and is reproduced in a coarse-grained mean-field model: self-consistent field theory (SCFT). Using further SCFT calculations, we study the distribution of the two copolymer species within the individual aggregates and discuss how this affects the self-assembled structures. We also investigate a binary mixture of lamella-formers of different molecular weights and find that this system forms vesicles with a wall thickness intermediate to those of the vesicles formed by the two copolymers individually. This result is also reproduced using SCFT. Finally, a mixture of sphere-former and a copolymer with a large hydrophobic block is shown to form a range of structures, including novel elongated vesicles.


McLeish, T. C. B., Butler, M. F., Buzza, D. M. A., Atkins, D., Furzeland, S., Schuetz, P., & Greenall, M. J. (2011). Controlling the self-assembly of binary copolymer mixtures in solution through molecular architecture. Macromolecules, 44(13), 5510-5519.

Journal Article Type Article
Acceptance Date Jul 12, 2011
Publication Date Jul 12, 2011
Print ISSN 0024-9297
Electronic ISSN 1520-5835
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 44
Issue 13
Pages 5510-5519
Keywords Inorganic Chemistry; Organic Chemistry; Materials Chemistry; Polymers and Plastics
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