The fine crystals of an Al-containing layered silicate, whose negative layer charge is generated by an isomorphous substitution in the tetrahedral SiO4 framework, successfully grew on monodisperse amorphous silica microspheres with diameters of 1.0 and 2.6 μm. The fine, plate-like crystals were observed to thoroughly cover the surface of the silica spheres, irrespective of their size, by the hydrothermal reactions of the silica powder in aqueous alkali solution containing Al and Mg ions in a rotating Teflon-lined autoclave. The crystal size increased when the concentration of the precursors was low. The presence of fluorine in the reaction media enlarged the crystalline phase in the direction of the layer stacking while reducing the plate size. The difference in the crystal size affected the kinetics on the hinokitiol desorption in n-hexane from the layered silicates modified with organoammonium ions. The organically modified layered silicate behaved as an exfoliated nanosheet in the nonpolar solvent. The less harmful elements in this hybrid suggest that it can be used in cosmetic and pharmaceutical applications as a drug support, without flaking off the fine layers on the microspherical substrates.
This study aims to investigate the growth of a cation-exchangeable hydrated layer on the surface of mica-type silicates based on a synthetic fluorophlogopite and a natural muscovite. Through the reaction of a synthetic fluorophlogopite using LiF, MgCl2, and a silica sol in water at 373 K for 48 h in the presence of urea, a hydrated phyllosilicate was formed on the fluoromica. As a result of examining the reaction in the alkali solution in the absence of Mg2+, the uptake of the silica sol would be included as a chemical process to begin the crystallization on fluorophlogopite because the lithium and ammonium ions (generated by urea hydrolysis) are known to contribute to enhanced adsorption. We found that the urea hydrolysis increased the pH, which, in turn, assisted the formation of magnesium hydroxide after the isomorphic substitution of Li+ for Mg2+. Bridging tetrahedral SiO4 with a magnesium–lithium double hydroxide afforded a 1 nm silicate layer. This facilitated the hectorite-like hydrated silicate layer to adhere closely to both the crystal edge and the cleaved face of the synthetic mica, which was found to coat the surface homogeneously. Only surface crystals were found to form through this process. The layered silicates included exchangeable hydrated cations for the cation-exchange reactions to expand the interlayer space by a cationic surfactant, dimethyldistearylammonium. The layered silicate also adsorbed methylene blue as a cationic dye in the aqueous phase. Apart from fluoromica, the natural muscovite also provided the surface to grow hydrated silicate layers, as a crystal turned dense blue when reacted with methylene blue.
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