Structure and rheology of multi-chain amphiphilic block copolymers under shear in dilute solutions

TL;DR

This computational study investigates how multichain amphiphilic block copolymers self-assemble and behave rheologically under shear, revealing architecture-dependent network formation and flow properties crucial for designing drug delivery systems.

Contribution

It systematically analyzes the effects of chain architecture, length, composition, and shear rate on copolymer self-assembly and rheology using Brownian dynamics simulations.

Findings

Triblock copolymers form extensive 3D networks with higher viscosity.

Shear induces elongation and aggregation of micelles, with architecture-dependent structural changes.

Triblocks exhibit slower network relaxation and increased relaxation times with hydrophobic content.

Abstract

This study presents a computational investigation of self-assembly and rheological behaviour of multichain amphiphilic block copolymers under varying chain length, architecture, composition, and shear rate. Using Brownian dynamics (BD) simulations, we systematically examined bead-spring model multi-chain diblock and triblock copolymers with chain lengths of 12-48 beads, hydrophobic fractions (f) ranging from 0 to 1.0, and shear rates spanning 0-0.1 1/ns. In the dilute regime, results demonstrate that triblock copolymers form extensive 3D networks with bridging architectures through hydrophobic end blocks, achieving solution viscosities up to half an order of magnitude higher than diblock systems, with superior structural integrity under weak shear. At shear rate=0.003-0.01 1/ns, both chain architectures show increased gyration radius of individual chains within each micelle and decreased cluster counts, indicating aggregation of clusters prior to breakdown at higher shear rates. Shape anisotropy analysis reveals that triblocks develop highly elongated prolate structures (L1/L3 = 11) at high shear rates, while diblocks form more discrete micellar assemblies (L1/L3 = 7.5). Chain length analysis shows systematic increases in radius of gyration, with triblocks exhibiting an increase in cluster count, indicative of network percolation. Rheologically, triblock systems maintain lower crossover frequencies with increasing hydrophobic fraction, reflecting slower network relaxation versus diblocks. The terminal relaxation time of triblock copolymer systems increases with hydrophobic fraction due to double-ended hydrophobic bridging, while diblocks maintain stable values. These findings provide fundamental insights for the rational design of polymer-based drug carriers through architectural selection and flow conditions.