Formation of Diblock Copolymer Nanoparticles: Theoretical Aspects

TL;DR

This paper uses theoretical modeling to analyze how diblock copolymer nanoparticles form various shapes and internal structures depending on interaction parameters, size, and solvent preferences, aligning well with experimental observations.

Contribution

It provides a theoretical framework predicting nanoparticle shapes and internal morphologies based on key parameters, advancing understanding of diblock copolymer self-assembly.

Findings

NP aspect ratio varies non-monotonically with interaction parameter τ.

Solvent preference influences transition from ellipsoidal to onion-like structures.

Critical conditions for phase transitions between internal morphologies are identified.

Abstract

We explore the shape and internal structure of diblock copolymer (di-BCP) nanoparticles (NPs) by using the Ginzburg-Landau free-energy expansion. The self-assembly of di-BCP lamellae confined in emulsion droplets can form either ellipsoidal or onion-like NPs. The corresponding inner structure is a lamellar phase that is either perpendicular to the long axis of the ellipsoids (L$_\perp$) or forms a multi-layer concentric shell (C$_\parallel$), respectively. We focus on the effects of the interaction parameter between the A/B monomers $\tau$, and the polymer/solvent $\chi$, as well as the NP size on the nanoparticle shape and internal morphology. The aspect ratio ($l_{\rm AR}$) defined as the length ratio between the long and short axes is used to characterize the overall NP shape. Our results show that for the solvent that is neutral towards the two blocks, as $\tau$ increases, the $l_{\rm AR}$ of the NP first increases and then decreases, indicating that the NP becomes more elongated and then changes to a spherical NP. Likewise, decreasing $\chi$ or increasing the NP size can result in a more elongated NP. However, when the solvent has a preference towards the A or B blocks, the NP shape changes from striped ellipsoid to onion-like sphere by increasing the A/B preference parameter strength. The critical condition of the transition from an L$_\perp$ to C$_\parallel$ phase has been identified. Our results are in good agreement with previous experiments, and some of our predictions could be tested in future experiments.