In Situ Investigation of Si-TPA-MFI Crystallization Using (Ultra-) Small- and Wide-Angle X-ray Scattering

The formation of precursors and the growth and aggregation of silicalite-1 crystals using tetrapropylammonium as a template (Si-TPA-MFI) has been studied in situ using X-ray scattering techniques. Simultaneous smallangle and wide-angle X-ray scattering (respectively SAXS and WAXS) experiments using synchrotron light showed that the formation of amorphous colloidal aggregates in water clear synthesis mixtures was dependent on the alkalinity of the solutions. In situ time-resolved ultra-small-angle X-ray scattering (USAXS) showed the form factor oscillations of the growing crystals. Fitting of the USAXS patterns to the scattering pattern of spherical particles having a normal particle size distribution showed a linear growth of the average crystal diameter, which was approximately the same for both alkalinities studied. The final size of the crystals was highest for the synthesis mixture having the highest alkalinity, which can be explained in terms of number of viable nuclei formed. At the end of the linear growth the crystals form aggregates corresponding with a diffusion limited aggregation process (mass fractal dimension of 1.8).