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Self-assembly kinetics of miktoarm star polymers in diverse solvent environments: insights from dissipative particle dynamics simulations.

Devendra Kumar Verma,Awaneesh Singh

Published 2025 in Soft Matter

ABSTRACT

We present the self-assembly kinetics of miktoarm star polymers (MSPs) with compositional and topological asymmetries in various solvents using three-dimensional dissipative particle dynamics simulations. Morphological evolution, analyzed via radial distribution, spatial correlation functions, and domain growth exponents, reveals distinct structures driven by solvent-MSP interactions. Good solvents promote a mostly slow domain growth rate, resulting in a porous morphology, whereas poor solvents facilitate a faster growth rate and lead to denser and localized lamellar or cylindrical structures. Domain growth follows a power-law behavior with an exponent of nearly 1/3 in the early diffusive regime; however, the growth rate and saturation of the domain size vary with solvent quality. Topologically asymmetric MSPs form interconnected bicontinuous morphologies in good solvents and localized lamellae in poor solvents. The correlation function scaling deviates from universality in symmetric interactions but exhibits better collapse when one arm is solvophilic. Thermodynamic analysis shows that increasing solvophobicity reduces entropy, raises enthalpy, and thus influences self-assembly kinetics. These findings significantly improve our understanding of complex MSP self-assembly under different solvent conditions and offer pathways for designing polymeric materials with diverse functionalities.

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