Arrested coalescence behaviour of giant Pickering droplets and colloidosomes stabilised by poly(tert-butylaminoethyl methacrylate) latexes

Abstract

The coalescence of two oil droplets grown at pH 10 in the presence of lightly cross-linked 260 nm diameter charge-stabilised poly(tert-butylamino)ethyl methacrylate (PTBAEMA) latexes was monitored using a high-speed video camera. Three model oils (n-dodecane, isopropyl myristate and sunflower oil) were investigated, each in the absence and presence of an oil-soluble cross-linker [tolylene 2,4-diisocyanate-terminated poly(propylene glycol), PPG-TDI]. In the absence of PPG-TDI, rapid coalescence was observed for giant PTBAEMA-stabilised Pickering oil droplets, which exhibited faster coalescence times compared to bare oil droplets. However, an increase in the damping coefficients for coalescing Pickering droplets (compared to those of bare oil droplets) indicated PTBAEMA latex particle adsorption. Addition of PPG-TDI cross-linker to oil droplets in the absence of latex particles led to a reduction in the interfacial tension confirming its surface-active nature. The oil-soluble PPG-TDI reacts with the secondary amine groups on the PTBAEMA latex, producing giant colloidosomes that remain stable to coalescence when brought into contact. This stability to coalescence was not observed for bare oil droplets in the presence of PPG-TDI, confirming that the cross-linked latex particles at the interface provide the additional stability. Finally, interactions between asymmetric n-dodecane droplets were examined. Adding oil-soluble cross-linker to only one droplet resulted in “arrested coalescence” behaviour in the presence of PTBAEMA latex particles. In this context, the droplet ageing time was found to be critical and is attributed to the relatively slow particle adsorption kinetics. Ageing times of less than 60 s led to catastrophic droplet coalescence, whereas ageing times longer than 60 s indicated cross-linker diffusion from one droplet to the other, which produced inter-cross-linked colloidosomes. Arrested coalescence was only observed for ageing times of approximately 60 s.