Characterization of the volume fraction of soft deformable microgels by means of small-angle neutron scattering with contrast variation

The volume occupied by colloids in a suspension - namely the volume fraction - is the thermodynamic variable that determines the phase behavior of these systems. While for hard incompressible spheres this quantity is well defined, for soft compressible colloids such as microgels - polymeric crosslinked networks swollen in a good solvent - the determination of the real volume occupied by these particles in solution is particularly challenging. This fact depends on two aspects: first the surface and, therefore, the volume of the microgels is hard to define properly given their external fuzziness; second, microgels can osmotically deswell, deform or interpenetrate their neighbors, i.e. change their shape and size depending on the solution concentration. Here, the form factors of few hydrogenated microgels embedded in a matrix of deuterated but otherwise identical microgels are measured using small-angle neutron scattering with contrast variation. From the analysis of the scattering data, the variation of the volume of the microgels as a function of concentration is obtained and used to calculate the real microgel volume fraction in solution. Soft neutral microgels are shown to facet already at low concentrations while in contrast, harder microgels maintain their shape and change their volume.