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Journal Articles ACS Macro Letters Year : 2023

In situ monitoring of block copolymer self-assembly through controlled dialysis with light and neutron scattering detection

Abstract

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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Dates and versions

hal-03841722 , version 1 (07-11-2022)
hal-03841722 , version 2 (09-09-2023)

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Attribution - NonCommercial - NoDerivatives

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Martin Fauquignon, Lionel Porcar, Annie Brûlet, Jean-François Le Meins, Olivier Sandre, et al.. In situ monitoring of block copolymer self-assembly through controlled dialysis with light and neutron scattering detection. ACS Macro Letters, 2023, 12 (9), pp.1272-1279. ⟨10.1021/acsmacrolett.3c00286⟩. ⟨hal-03841722v2⟩
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