Kinetic Pathways to Diblock Copolymer Micelles via Thin Film Dissolution and Cosolvent Variation
Year: 2026
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide We investigate how processing pathways control micelle formation during dissolution of lamellar diblock copolymers using dissipative particle dynamics (DPD) simulations and DPD-self-consistent field theory (DPD-SCFT). Comparing thin film (TF) and cosolvent-assisted (CS) dissolution reveals fundamentally different micellization mechanisms and final states. In the TF pathway, dissolution proceeds through a metastable cylindrical intermediate that dictates final micelle dimensions. The lamellar melt first transforms into cylindrical micelles, which then fragment into spherical micelles. The final spherical radius is intrinsically linked to the cylinder radius by a constant ratio, R sphere ≈ 1.4 R cylinder . DPD-SCFT confirms that both cylinders and spheres are near their equilibrium dimensions. In contrast, CS dissolution produces kinetically trapped micelles with sizes significantly below equilibrium. Micellization is hindered by high free energy barriers to single-chain exchange and fusion. Growth occurs primarily via fusion, but increasing corona repulsion suppresses further coarsening, preventing equilibration. These results demonstrate that, when starting from a bulk copolymer phase, the metastable cylindrical intermediate plays a central role in determining final micelle size.
Source: Macromolecules
Institutions: California Institute of Technology, University of Minnesota
Language: English
Subfield: Materials Chemistry
Field: Materials Science
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
OpenAlex ID: W7156255707