The effects of surface functionalization on rheology, structure and transport properties of nanocomposites

In this thesis, the effects of surface functionalization using hydrophobic silanes on properties of nanocomposites comprising 42 nm silica particles suspended in a melt of polyethylene-glycol (PEG) are studied using rheological, static and dynamic x-ray scattering studies. The nanocomposites are studied in the low molecular weight unentangled (PEG-400) and high molecular weight entangled (PEG-20000) regimes. We find no differences in the properties of the bare and silanized particles in the low volume fraction regime up to where the interparticle separation distance h > 6Rg. In the region of 6Rg > h > 3Rg (5Rg > h > 3Rg, in case of entangled melts), we find substantial differences in the rheological, structure and transport properties when comparing the bare and silanized particles. In the unentangled melts, we observe up to four orders of magnitude drop in the viscosity of the composites at the highest levels of silanization and observe shear thinning behavior that is unlike what is universally seen for hard spheres. For the entangled melts, a yield stress is observed for the silanized particles that is absent in the case of the bare particles and there is a divergence in the elastic modulus in comparison to bare particles. We observe an anomalous speed up in the density relaxations and an associated maxima in structure properties in the case of unentangled melts which has been reported previously for particles experiencing soft repulsive potentials. A clear reentrant behavior in structure and transport properties is observed for bare particles in the entangled melts that have been previously reported for particles interacting with soft repulsive potentials such as square shoulder and ramp potentials. In the silanized systems, the density relaxation times although lower than bare particles, is ii unaffected by increasing volume fraction up to h ~ 3Rg and is decoupled from the structure properties which are non-monotonic similar to bare particles. In the region of h < 3Rg, we find that the bare and silanized particles are comparable in structural properties for unentangled melts. In the case of entangled melts, the rheological, structure and transport properties of the bare and silanized particles are similar and indicative of strong localization of particles interacting with harsh potentials expected of core-core interactions.