Kinetics analysis of colloidal crystallization of silica spheres modified with polymers on their surfaces in acetonitrile

The nucleation and growth rates in the colloidal crystallization of silica spheres (136 nm in diameter) modified with polymers on their surface were measured by time-resolved reflection spectroscopy. The polymers were poly(maleic anhydride-co-styrene) [P(MA-ST)] and poly(methyl methacrylate) (PMMA). The induction period for nucleation decreased sharply when the sphere concentration increased. The crystal growth process consisted of a fast growing step leading to metastable crystals (rate v(1)) and a slow growth rate accompanied by the formation of stable crystals. The crystal size of the P(MA-ST)/SiO2 particles decreased from 0.4 to 0.06 mm, whereas v, increased from 13 to 37 mum/s, when the particle concentration increased. The slow step was also observed for almost all the samples but was not analyzed since the rate was too small. For PMMA/SiO2 dispersions, the crystal size (0.17-0.3 mm) and v(1) (43-166 mum/s) did not show any relation to the particle concentration but showed a linear relationship with the molecular weight of PMMA. These results suggest the important role of the excluded-volume effects of the polymer layers around the silica surface. The contribution of the repulsion due to the electrical double layers is still effective in the colloidal crystallization in acetonitrile.