In Situ Monitoring of Block Copolymer Self-Assembly via Solvent Exchange through Controlled Dialysis with Light and Neutron Scattering Detection
- Martin Fauquignon*
- Lionel Porcar*
- Annie BrûletAnnie BrûletLaboratoire Léon Brillouin, Commissariat à l’Energie Atomique et aux Energies Alternatives (CEA) Saclay, F-91191 Gif-sur-Yvette, FranceMore by Annie Brûlet
- Jean-François Le Meins
- Olivier Sandre
- Jean-Paul Chapel
- Marc SchmutzMarc SchmutzUniversité de Strasbourg, CNRS, Institut Charles Sadron, UPR 22, F-67034 Strasbourg, FranceMore by Marc Schmutz
- , and
- Christophe Schatz*
Solution self-assembly of amphiphilic block copolymers (BCs) is typically performed by a solvent-to-water exchange. However, BC assemblies are often trapped in metastable states depending on the mixing conditions such as the magnitude and rate of water addition. BC self-assembly can be performed under near thermodynamic control by dialysis, which accounts for a slow and gradual water addition. In this Letter we report the use of a specifically designed dialysis cell to continuously monitor by dynamic light scattering and small-angle neutron scattering the morphological changes of PDMS-b-PEG BCs self-assemblies during THF-to-water exchange. The complete phase diagrams of near-equilibrium structures can then be established. Spherical micelles first form before evolving to rod-like micelles and vesicles, decreasing the total developed interfacial area of self-assembled structures in response to increasing interfacial energy as the water content increases. The dialysis kinetics can be tailored to the time scale of BC self-assembly by modifying the membrane pore size, which is of interest to study the interplay between thermodynamics and kinetics in self-assembly pathways.
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