Publication details for Prof Tom McLeishGreenall, Martin J., Schuetz, Peter, Furzeland, Steve, Atkins, Derek, Buzza, D. Martin A., Butler, Michael F. & McLeish, Tom C.B. (2011). Controlling the Self-Assembly of Binary Copolymer Mixtures in Solution through Molecular Architecture. Macromolecules 44(13): 5510-5519.
- Publication type: Journal papers: academic
- ISSN/ISBN: 0024-9297, 1520-5835
- DOI: 10.1021/ma2008546
- View online: Online version
- Durham research online: DRO record
Author(s) from Durham
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.