The objective of the study was to contribute to the understanding of the influence of the structure and the 2:1 layer dimension of smectites on cation exchange capacity (CEC) reduction and the hydration behavior of Li-saturated smectites after heating. Five montmorillonites extracted from bentonites of different provenance were saturated with Li+ and heated to 300°C. Initial montmorillonites and montmorillonites with reduced layer charge (RCM) were characterized by comprehensive mineralogical analysis supplemented by CEC measurements, surface-area measurements by Ar adsorption, and 7Li, 27Al, and 29Si magic-angle spinning nuclear magnetic resonance spectroscopy (MAS NMR). The CEC of the initial montmorillonites varied between 89 and 130 cmol(+)/kg while the CEC of the RCM prepared at 300°C varied between 8 and 25 cmol(+)/kg. The lateral dimension of the 2:1 layers varied between 70 and 200 nm. The greatest decrease in CEC was observed for the montmorillonite with the largest diameter of the 2:1 layers and the smallest decrease was observed for the montmorillonite with the smallest diameter of the 2:1 layers. 7Li MAS NMR revealed an axially symmetric chemical environment of the hydrated interlayer Li+ with ηΔ = 0 for the chemical shift anisotropy tensor for unheated montmorillonites with >33% tetrahedral layer charge (ξ). The chemical environment is typical of innersphere hydration complexes of interlayer Li+. An axially non-symmetric chemical environment of the interlayer Li+ with ηCS of close to one was observed for all RCM. While the remaining CEC of RCM prepared at 300°C reflected the variable CEC at the edges, and thus the lateral size or aspect ratio of the 2:1 layers, the hydration complex of interlayer Li+ was strongly determined by the isomorphic substitutions in the dioctahedral 2:1 layers.

In recent years KAlSiO4 polymorphs have become minerals of interest from an industrial point of view; they have various applications in technological and medical fields. The costs of synthesis processes are often significant and so, in the present study, an attempt was made to develop a new synthesis protocol using a widely available and inexpensive, natural starting material. The KAlSiO4 polymorphs synthesized here were kalsilite and KAlSiO4-01 — 01 refers to the high-temperature polymorph of KAlSiO4 (Cook et al., 1997; Gregorkiewitz et al., 2008; Kremenovic et al., 2013). KAlSiO4 polymorphs were synthesized using kaolin; the effects of time and temperature on the synthesis process were investigated. A solid-state synthesis protocol was developed which required the mixing of the calcined kaolin with K2CO3 in stoichiometric proportions at temperatures of 700 and 800°C at atmospheric pressure. Crystallization of kalsilite at 700°C was demonstrated while that of KAlSiO4-01 was revealed at 800°C. Synthetic kaliophilite H2 was found in both of the experiments as a metastable phase. The products of synthesis were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), inductively coupled plasma optical emission spectrometry (ICP-OES), infrared spectroscopy (IR), and 29Si magic-angle spinning solid-state nuclear magnetic resonance spectroscopy (29Si MAS NMR). Calculation of cell parameters (through Rietveld refinement) and the density and specific surface area of the phases synthesized was also achieved. The amount of amorphous phase in the synthesis powders was estimated by means of quantitative phase analysis using the combined Rietveld and reference intensity ratio methods. In particular, the results of the spectroscopic, chemical, and morphological characterizations are in agreement with the data available for these minerals in the literature, thus confirming the effectiveness of the experimental protocol. The quantitative phase analysis (QPA) also indicated the high purity of the powders synthesized, thus allowing for industrial applications.

Hydrothermal syntheses of the magadiite, a layered silicate structure, were conducted in the presence of a heteroatom source (SnCl4.5H2O) with the intention of investigating its influence on the resulting material, as well as the possibility of isomorphous replacement of Si by Sn atoms in the abovementioned structure. For comparison, unmodified magadiite, Al-containing magadiite, and impregnated magadiite were synthesized. The magadiite structure was identified for samples with Sn/Si ratios up to 0.015. Synthetic methods applied to Sn-modified materials were found to be unsuitable for the introduction of Al. The characterization methods used were X-ray diffraction, temperature-programmed reduction, and 29Si magic angle spinning nuclear magnetic resonance and these revealed the substitution of Si by Sn in the silica layers. No additional acid centers on the surfaces of the modified samples were detected, suggesting the presence of the desired four-coordinate Sn in the silica layers.