Compression effects on the phase behavior of microgel assemblies

Microgels are a class of colloids that are mechanically soft, and while in many cases can behave similarly to their hard-sphere counterparts, their interaction potentials are quite different. The softness of the interaction between microgels makes them capable of deformation and compression into more concentrated assemblies. This concentrated regime is interesting because little, if any, experimental work has been done to see how the bulk properties of soft-sphere assemblies deviate from those of hard-spheres at the point where their interaction potentials begin to diverge. In this thesis the effects on assembly phase behavior and dynamics of both particle compression and softness of the interaction potential are addressed. Poly(N-isopropylacrylamide) (pNIPAm) microgels are an excellent model system in which to study these effects. The thermoresponsivity of the polymer provides the experimentalist with a dial to tune the volume fraction of an assembly, while maintaining a constant particle number density in the system. Optical microscopy, particle tracking analysis and rheology have been used to investigate the effects of packing and particle structure on equilibrium phase behavior and localized perturbations to the phase of the assembly of this soft-sphere system. It has been elucidated from these experiments and others involving deswelling of large microgel particles in the presence of high concentrations of smaller microgels, that the soft, repulsive interaction between microgels is caused by a longer-range repulsion than was previously believed. The particles are acting on each other from a distance through the osmotic pressure of the assembly, which causes each particle to deswell without coming into direct contact with a neighboring particle.Ph.D.Committee Chair: Lyon, L. Andrew; Committee Member: Breedveld, Victor; Committee Member: Hernandez, Rigoberto; Committee Member: Srininvasarao, Mohan; Committee Member: Weeks, Eric R