The role of ions in the self healing behavior of soft particle suspensions
Significance Understanding when a material crystallizes is of fundamental importance in condensed matter. In many materials, the presence of point defects suppresses crystallization. Surprisingly, colloidal hydrogels can overcome this limitation: A small number of large microgels can spontaneously deswell to fit in the crystal lattice of smaller microgels, thus avoiding the occurrence of point defects. We find that this unique particle deswelling is due to an osmotic pressure difference between the inside and the outside of the microgels resulting from the overlap of counterion clouds of neighboring particles. When this pressure difference exceeds the bulk modulus of the large microgels, these shrink, enabling crystallization without point defects. Impurities in crystals generally cause point defects and can even suppress crystallization. This general rule, however, does not apply to colloidal crystals formed by soft microgel particles [Iyer ASJ, Lyon LA (2009) Angew Chem Int Ed 48:4562 4566] as, in this case, the larger particles are able to shrink and join the crystal formed by a majority of smaller particles. Using small angle X ray scattering, we find the limit in large particle concentration for this spontaneous deswelling to persist. We rationalize our data in the context of those counterions that are bound to the microgel particles as a result of the electrostatic attraction exerted by the fixed charges residing on the particle periphery. These bound counterions do not contribute to the suspension osmotic pressure in dilute conditions, as they can be seen as internal degrees of freedom associated with each microgel particle. In contrast, at sufficiently high particle concentrations, the counterion cloud of each particle overlaps with that of its neighbors, allowing these ions to freely explore the space outside the particles. We confirm this scenario by directly measuring the osmotic pressure of the suspension. Because these counterions are then no longer bound, they create an osmotic pressure difference between the inside and outside of the microgels, which, if larger than the microgel bulk modulus, can cause deswelling, explaining why large, soft microgel particles feel the squeeze when suspended with a majority of smaller particles. We perform small angle neutron scattering measurements to further confirm this remarkable behavior.
Proceedings of the National Academy of Sciences