Cristaloquímica de esmectitas dioctaédricas em bentonitas brasileiras

Abstract

Bentonites are mineral inputs of great industrial interest due to the physicochemical properties of clay minerals from the smectite group. These properties, resulting from the complex crystal chemistry and small particle size of smectites, include various layer charge, swelling capacity, and cation exchange capacity. In Brazil, the main bentonite deposits are located in the municipality of Boa Vista, Paraíba, which accounts for >70% of the country’s production. However, the progressive depletion of these varieties has motivated the search for new deposits. Among them, the Formosa deposit, in the state of Maranhão, stands out. Although both the Boa Vista and, to a lesser extent, the Formosa bentonites have been extensively studied in their <2 μm or coarser fractions, the crystal chemistry of their smectites has not yet been fully elucidated. This is due not only to the typical chemical and structural complexity of smectites, but also to the difficulty of obtaining pure smectite phases and the interference of accessory minerals. In this context, this thesis presents a detailed study of the crystal chemistry of smectite from the Formosa deposit, comparing it with three commercial varieties from Boa Vista: Bofe, Chocolate, and Verde Lodo. The <2 μm, 0.1-2 μm, and <0.1 μm fractions were analyzed, with the latter being the main focus of the study. The analyses included XRD (Rietveld method), FTIR, TEM-EDS, SEM, XRF, AAS, TG, and Mössbauer spectroscopy. These smectites, previously described as montmorillonites, also exhibit significant tetrahedral layer charge. In fact, the four samples show a tetrahedral charge of approximately 0.15 per half unit cell, sufficient to induce swelling after the Hofmann-Klemen treatment. The octahedral symmetry of all four samples was trans-vacant, influenced by both the Fe content and the tetrahedral charge. The structural and chemical similarities between the Formosa and Boa Vista smectites, along with similar smectite content in the <2 μm and <0.1 μm fractions – as quantified by the Rietveld method – demonstrated that the Formosa deposit is a potential alternative to the Boa Vista bentonites.