Effect of PEG on rheology and stability of nanocrystalline titania hydrosols

Rheological behaviour and stability of TiO 2 colloidal dispersions in water are explained through the aggregation of primary nanoparticles and change in the fractal dimension of aggregates. Very stable titania hydrosols were prepared by fast hydrolysis of titanium isopropoxide in a large excess of water. XRD patterns show that these sols contain nanocrystals (5–6 nm) of anatase (70%) and brookite (30%). TEM images indicate that these primary particles form aggregates whose mean hydrodynamic diameter, determined by photon correlation spectroscopy, is in the range of 80–90 nm. The flow curves of these colloids, recorded for several volume fractions of nanoparticles, can be perfectly fitted, in the range 0–100 s −1, with a power-law model. In this range the behavior is Newtonian but for larger shear rates a shear thinning is observed. The viscosity dependence on particle concentration can be predicted by a Batchelor-type model were the volume fraction of particles is replaced by an effective volume fraction of aggregates, taking into account their fractal dimension. Addition of polyethylene glycol (PEG 2000) induced a marked decrease (more than 50%) of the sol viscosity down to a minimum. This is explained by assuming that PEG adsorbs on the surface of TiO 2 particles producing stabilization by steric effects and leading to formation of more compact aggregates. Without PEG the sol viscosity strongly decreases on aging. This effect is not caused by the growth of primary particles. It is rather interpreted as a progressive reorganization of the aggregates toward a more compact packing.