RESUMEN
The phase behavior of supersoft spheres is explored using solutions of ultralow cross-linked poly(N-isopropylacrylamide)-based microgels as a model system. For these microgels, the effects of the electric charges on their surfaces can be neglected and therefore only the role of softness on the phase behavior is investigated. The samples show a liquid-to-crystal transition at higher volume fraction with respect to both hard spheres and stiffer microgels. Furthermore, stable body centered cubic (bcc) crystals are observed in addition to the expected face centered cubic (fcc) crystals. Small-angle x-ray and neutron scattering with contrast variation allow the characterization of both the microgel-to-microgel distance and the architecture of single microgels in crowded solutions. The measurements reveal that the stable bcc crystals depend on the interplay between the collapse and the interpenetration of the external shell of the ultralow cross-linked microgels.
RESUMEN
Microgels are solvent-swollen nano- and microparticles that show prevalent colloidal-like behavior despite their polymeric nature. Here we study ultra-low crosslinked poly(N-isopropylacrylamide) microgels (ULC), which can behave like colloids or flexible polymers depending on dimensionality, compression or other external stimuli. Small-angle neutron scattering shows that the structure of the ULC microgels in bulk aqueous solution is characterized by a density profile that decays smoothly from the center to a fuzzy surface. Their phase behavior and rheological properties are those of soft colloids. However, when these microgels are confined at an oil-water interface, their behavior resembles that of flexible macromolecules. Once monolayers of ultra-low crosslinked microgels are compressed, deposited on solid substrate and studied with atomic-force microscopy, a concentration-dependent topography is observed. Depending on the compression, these microgels can behave as flexible polymers, covering the substrate with a uniform film, or as colloidal microgels leading to a monolayer of particles.
