Particles in complex fluids
Zand, Daniëlle D. van ’t
This thesis describes experimental studies of colloidal particles dispersed in solvents which themselves have phase transitions. One common definition of soft matter is: a material characterized by a mesoscopic length scale. This length scale is, for example, the colloid size or the ordered domain size. Here we combine a complex host with one characteristic length scale with dispersed particles that have a different size. It might be anticipated that new behaviour will occur. Two limits of particle characteristics are probed: the case of dilute sterically-stabilized particles and the case of a weak gel of attractive particles. The two systems are polymer particles dispersed in a phaseseparating microemulsion and silica nanoparticles dispersed in a low molecular weight liquid crystal. In each system a temperature driven phase transition plays a crucial role. In the microemulsion case we observe how transitional and pre-transitional phenomena create effective interactions between particles and how new behaviour emerges in the host solvent in the late stage of the phase separation. We show that the pre-transitional clustering of the PMMA particles is due to an adsorbed layer of dodecane. Subsequently heterogeneous nucleation of the gas phase is seen. After phase separation has occurred in off-critical samples the particles remain in either the continuous or dispersed phase depending on the original microemulsion composition. In the late stage of the phaseseparation the coalescence and coarsening behaviour changes significantly, after more material exchange between the phases has taken place. This behaviour is reminiscent of viscoelastic phase separation in polymer based samples. In the liquid crystal case we discover the anisotropy of the liquid crystal persists over large length scales and modifies the local dynamics of the gel. Using electron microscopy and scattering techniques we demonstrate that the silica embedded in the liquid crystal forms agglomerates with a fractal structure. Rheological characterization demonstrates that the resulting composite is a gel. Investigation of the composite’s local dynamics using x-ray photon correlation spectroscopy shows anisotropy and intermittency in the dynamics on significant length scales. In both systems we have studied new behaviour seen due to the influence of one component on the dynamic characteristics of the other The pre- and post- phase transition phenomena are only crucial in the microemulsion case where the particles have purely repulsive interactions. Our results illustrate the subtle balances that occur in soft composite systems.