Structural changes in nanoparticle-hydrogel composites at very low filler concentrations

We study the enhancement of the stiffness of two families of hydrogels (polyacrylamide, PAAm, and polydimethylacrylamide, PDMA) due to the additions of very small amounts of silica nanofillers. It is well established that high concentrations of silica nanoparticles enhance the toughness of both hydrogel types, but significantly more for the PDMA based gels that adsorb readily to silica surfaces. In order to decouple the structural changes in the gels that stem either from polymerization kinetics or from the interactions between nanofillers and polymers, we use a photoinitiator for the polymerization of the composite gels that promotes the structural homogeneity of the hydrogels. We characterize both the mechanical and structural properties of the composite hydrogels as a function of nanofiller concentration, by calculating the single particle diffusion of inert polystyrene tracer particles of three different sizes. In agreement with previous experiments, we find that silica nanoparticles increase the stiffness of PAAm gels more than expected for passive fillers. Surprisingly, we find that a small addition of silica nanoparticles during gel polymerization to PDMA based hydrogels softens them. We attribute this effect to an increase of the average mesh size of the gel, allowing particles of 0.49 μm in diameter to diffuse normally through the gel, but restricting the motion of larger particles. A further increase in silica nanoparticle concentration results in the expected stiffening of the gel. PDMA based composites with a large mean pore size, as reported here, may find applications in particle separation and gentle fixation of microorganisms and cells.