Thermal analysis of hexadecyltrimethylammonium-montmorillonites: Part 2. Thermo-XRD-spectroscopy-analysis

Na-montmorillonite (Na-MONT) was loaded with hexadecyltrimethylammonium cations (HDTMA) by replacing 41 and 90% of the exchangeable Na with HDTMA. The organoclays were labeled OC-41 and OC-90, respectively. Freeze-dried Na-MONT, OC-41, and OC-90 were heated in air at 150, 250, 360, 420, 550, 700, and 900 °C. The thermally treated samples were suspended in water, air-dried, and desiccated over silica during 40 days. All samples were diffracted by X-ray and fitting calculations were performed on each diffractogram. These calculations gave information on basal spacings, relative concentrations, and homogeneity of the different tactoids obtained at each temperature, before and after suspending and desiccating. HDTMA-MONT tactoids with spacing ≥1.41 nm appeared between 25 and 250 °C. OC-41 or OC-90 intercalated monolayers or bilayers of HDTMA, respectively. At 250 °C OC-41 was air-oxidized to a smaller extent than OC-90, resulting in charcoal-MONT tactoids. With further heating the organic matter was gradually oxidized and at 700 °C both clays were collapsed. During the thermo-XRD-analysis of both organoclays three types of charcoal-MONT complexes appeared: (1) LTSC-MONT tactoids with a basal spacing 1.32–1.39 nm, between 250 and 420 °C in both clays; (2) HTSC-α-MONT tactoids with spacing 1.22–1.28 nm, between 360 or 250 and 500 or 550 °C in OC-41 or OC-90, respectively; (3) HTSC-β-MONT with spacing 1.12–1.18 nm, between 360 and 550 °C in both clays, where LTSC and HTSC are low- and high-temperature stable charcoal, respectively. HTSC-β-MONT differs from HTSC-α-MONT by having carbon atoms keying into the ditrigonal holes of the clay-O-planes.