Silica polymerization and nanocolloid nucleation and growth kinetics in aqueous solutions

Amorphous silica precipitation from aqueous solutions at low temperatures (<100 °C) involves the initial nucleation and growth of silica polymers followed by aggregation, cementation and recrystallization to form opaline silica. In this study, silica polymerization was studied at temperature 23–80 °C, pH 2.48–9.65, and ionic strength 0.01–0.53 mol kg−1. Measured changes in the concentration of monomeric silica (SiO2(mono)) were fit assuming the polymerization reaction is fourth-order with respect to the difference between the concentration of silicic acid (Si(OH)4(aq)) and its concentration at equilibrium (Si(OH)4(aq)eq) with respect to amorphous silica:r=-k4AsmSi(OH)4(aq)-mSi(OH)4(aq)eq4where r is the overall rate of the reaction, As is the specific surface area of the formed polymers, calculated assuming particle-size-dependent solubility and a spherical polymer geometry, and k is the rate constant. The rate constant at zero ionic strength is given by:k0=Aexp-Ea/RTaOH-nwhere A is a pre-exponential constant (0.3822 mmol−3 cm−2 s−1), Ea is the activation energy (29.87 kJ mol−1) and n is equal to −0.80. The overall rate constant as a function of ionic strength (I) is given by:k4=k0Imwhere m is equal to 0.65. The rate constant increases by approximately six orders of magnitude from pH of 2 to 10 and one order of magnitude between temperature ∼ 20 and 80 °C. However, hydrolysis of silicic acid (Si(OH)4(aq)) at pH above ∼8 decreases the relative abundance of Si(OH)4(aq) while increasing the solubility of amorphous silica, thereby decreasing the rate of silica polymerization. The inferred reaction order is consistent with a reaction mechanism rate-limited by the formation of the cyclic tetramer across a wide range of pH. The time-dependence of the specific surface area during polymerization reflects the formation of critical nuclei towards the beginning of the polymerization process and Ostwald ripening of larger polymers towards the end of the polymerization process. The developed rate equation can predict rates of silica polymerization across a wide range of aqueous solution compositions.