Pluronic Induced Interparticle Attraction and Re-entrant Liquid-Liquid Phase Separation in Charged Silica...

Tuning surface properties of nanoparticles by introducing charge, surface functionalization, or polymer grafting is central to their stability and applications. Here, we show that introducing non-DLVO forces like steric and hydrophobic effects in charged silica nanoparticle suspensions through interaction with a nonionic surfactant brings about interesting modulations in their interparticle interaction and phase behavior. The Ludox TM-40 negatively charged silica suspensions thus exhibit liquid-liquid phase separation driven by the onset of interparticle attraction in the system in the presence of the triblock copolymer Pluronic P123. The observed phase separations are thermoresponsive in nature, as they are associated with lower consolute temperatures and a re-entrant behavior as a function of temperature. The nanoparticle-Pluronic system thus undergoes transformation from one-phase to two-phase and then back to one-phase with monotonic increase in temperature. Evolution of the interparticle interaction in the composite system is investigated by dynamic light scattering (DLS), small angle neutron scattering (SANS), zeta potential, rheological, and fluorescence spectroscopy studies. Zeta potential studies show that the charge interaction in the system is partially mitigated through adsorption of a Pluronic micellar layer on the nanoparticle surfaces. Contrast-matching SANS studies suggest that hydrophobic interactions between the adsorbed micellar layer bring about the onset of interparticle attraction in the system. The results are unique and not reported hitherto in charged silica nanoparticle systems.