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Stable in bulk and aggregating at the interface: comparing core-shell nanoparticles in suspension and at fluid interfaces
Siddarth Ayakulangara Vasudevan, Astrid Rauh, Lorenzo Barbera, Matthias Karg, Lucio Isa:
Langmuir, 34, 886-895 (2018)
doi: 10.1021/acs.langmuir.7b02015

Colloidal particles are extensively used to assemble materials from bulk suspensions or after adsorption and confinement at fluid interfaces, e.g. oil-water interfaces. Interestingly, and often underestimated, optimizing interactions for bulk assembly may not lead to the same behavior at fluid interfaces. In this work, we compare model composite nanoparticles with a silica core coated by a poly-N-isopropylacrylamide hydrogel shell in bulk aqueous suspensions and after adsorption at an oil-water interface. Bulk prop- erties are analyzed by confocal differential dynamic microscopy, a recently developed technique that allows simultaneously obtaining structural and dynamical information up to high volume fractions. The results demonstrate excellent colloidal stability and absence of aggregation in all cases. The behavior at the interface, investigated by a range of complementary approaches, is instead different. The same hydrogel shells that stabilize the particles in bulk deform at the interface and induce attractive capillary interactions, which lead to aggregation even at very low area fractions (surface coverage). Upon further compression of a particle-laden interface, a structural transition is observed where closely packed particle aggregates form. These findings emphasize the manifestation of different, and possibly unexpected, responses for sterically stabilized nanoparticles in bulk and upon interfacial confinement.