Spontaneous deswelling of microgels controlled by counterion clouds

Concentrated poly(N-isopropylacrylamide) (pNIPAM) microgel suspensions at a fixed temperature below the deswelling transition of pNIPAM exhibit spontaneous particle deswelling. The microgels deswell before they are in direct contact and in polydisperse suspensions this deswelling is most pronounced for the largest microgel particles; as a consequence, the polydispersity of the suspension is reduced. Recently, we presented a model for this spontaneous deswelling that is based on the presence of counterions originating from charged groups on the surface of the pNIPAM microgels [A. Scotti et al., Proc. Natl. Acad. Sci. USA 113, 5576 (2016)]. Here we present numerical Poisson-Boltzmann calculations of the electrostatic potential and osmotic pressure inside and outside a pNIPAM microgel that could trigger the observed deswelling at high particle concentrations.