Organic versus hybrid coacervate complexes: co-assembly and adsorption properties

Abstract

We report the co-assembly and adsorption properties of coacervate complexes made from polyelectrolyte–neutral block copolymers and oppositely charged nanocolloids. The nanocolloids put under scrutiny were ionic surfactant micelles and highly charged 7 nm cerium oxide (CeO₂) nanoparticles. Static and dynamic light scattering was used to investigate the microstructure and stability of the organic and hybrid complexes. For five different systems of nanocolloids and polymers, we first demonstrated that the electrostatic complexation resulted in the formation of stable core–shell aggregates in the 100 nm range. The microstructure of the CeO₂-based complexes was resolved using cryogenic transmission electronic microscopy (Cryo-TEM), and it revealed that the cores were clusters made from densely packed nanoparticles, presumably through complexation of the polyelectrolyte blocks by the surface charges. The cluster stability was monitored by systematic light scattering measurements. In the concentration range of interest, c = 10⁻⁴–1 wt.%, the surfactant-based complexes were shown to exhibit a critical association concentration (cac) whereas the nanoparticle–polymer hybrids did not. The adsorption properties of the same complexes were investigated above the cac by stagnation point adsorption reflectometry. The adsorbed amount was measured as a function of time for polymers and complexes using anionically charged silica and hydrophobic poly(styrene) substrates. It was found that all complexes adsorbed readily on both types of substrates up to a level of 1–2 mg m⁻² at stationary state. Upon rinsing however, the adsorbed layer was removed for the surfactant-based systems, but not for the cerium oxide clusters. As for the solution properties, these finding were interpreted in terms of a critical association concentrations, which are very different for organic and hybrid complexes. Combining the efficient adsorption and strong stability of the CeO₂-based core–shell hybrids on various substrates, it is finally suggested that these systems could be used appropriately for coating and anti-biofouling applications.