Silica Polymerization from Supersaturated Dilute Aqueous Solutions in the Presence of Alkaline Earth Salts.

The early stages of silica polymerization in aqueous solution proceed according to a mechanism based on three steps: nucleation, particle growth, and agglomeration of the particles. Application of time-resolved static and dynamic light scattering as a powerful in situ technique in combination with spectrophotometric analysis of the monomer consumption based on the molybdenum blue method was carried out to further investigate this 3-step process. Experiments were carried out at four different initial silicic acid contents covering a range between 350 and 750 ppm in the presence of either 10 mM NaCl or 5 mM of a mixture of CaCl2 and MgCl2 . The process in all cases was initiated with a drop of pH to 7. Addition of the salts made possible an analysis of the impact of an electrolyte on the process. Independent of the presence or absence of salt, particle growth in step two proceeded as a monomer-addition process without being interfered significantly by Ostwald-ripening. The growing particles were compact with a homogeneous density. The size of the particles approached final values between 5 and 20 nm with the actual value increasing with decreasing initial silicic acid content. Above a certain concentration of initial silica content, which depends on the level of added salt, particle-particle interactions caused agglomeration. The presence of electrolyte shifted this level from ∼2000 ppm to a range between 500 and 750 ppm. The resulting agglomerates had a fractal dimension of 2. Independent of the conditions, particle growth could be described with a simple nucleation and growth model.