RESUMO
Suspensions of microgel particles undergo a transition from liquid-like to solid-like mechanics upon increase of the microgel packing fraction. We study the opposed effects of the microgel softness and size on this transition. We tune the softness of the microgels by varying their polymer crosslinking density, while we simultaneously and independently vary their size and the contribution of Brownian particle motion by investigating two sets of colloidal-scale microgels synthesized by precipitation polymerization, along with one set of granular-scale microgels prepared by droplet-templated polymerization in microfluidic devices. We find that the microgel packing fraction at which the liquid-to-solid transition occurs depends on both the size and the softness of the microgel particles: small and soft microgels undergo this transition at much larger packing fractions than stiff microgels of the same size and than larger microgels with the same softness. This work suggests a systematic strategy to quantitatively predict this transition.
RESUMO
Polymer-network gels often exhibit local defects and spatial heterogeneity of their cross-linking density, which may differently affect their elasticity on microscopic and macroscopic scales. To appraise this effect, we prepare polymeric gels with defined extents of nanostructural heterogeneity and use atomic force microscopy to probe their local microscopic Young's moduli in comparison to their macroscopic elastic moduli measured by shear rheology. In this comparison, the moduli of the heterogeneous gels are found to be progressively smaller if the length scale of the probed gel region exceeds the size of the purposely imparted polymer-network heterogeneities. This finding can be explained with a conceptual picture of nonaffine deformation of the densely cross-linked polymer network domains in the heterogeneous gels.
