Thermogravimetric analysis of layered double hydroxides intercalated with sulfate and alkaline cations [M62+Al3(OH)18][A+(SO4)2] 12H2O (M2+ = Mn, Mg, Zn; A+ = Li, Na, K)

The synthesized phases with chemical composition $$\left[ {{\text{M}}^{2 + }_{6} {\text{Al}}_{3} \left( {\text{OH}} \right)_{18} } \right]\left[ {{\text{A}}^{ + } \left( {{\text{SO}}_{4} } \right)_{2} } \right]12{\text{H}}_{2} {\text{O}}$$ (M2+ = Mn, Mg, Zn; A+ = Li, Na or K) were evaluated in relation to their thermal behavior by thermogravimetric analysis (TGA), X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FTIR). In the shigaite (M2+ = Mn), natroglaucocerinite (M2+ = Zn) and motukoreaite (M2+ = Mg) phases, the TGA measurements indicated that all samples were dehydrated up to 200 °C in two steps, followed by dehydroxylation above 300 °C. After the thermal treatment at 1000 °C, formation of oxides/spinels were observed for the shigaite and natroglaucocerinite phases, while for motukoreaite, oxides, spinels and MgSO4 were detected. XRD indicated a reduction in the basal distance from around 11 A for the fully hydrated phases to around 7 A for the dehydrated phases. The thermal treatments of some samples at 100 °C, 150 °C and 200 °C indicated that in all phases, intercalated sulfate and alkaline metal ions can be dehydrated and rehydrated. As indicated by FTIR, at 200 °C sulfate could be grafted to the layers and at 300 °C, for all the phases, a stable mixture of amorphous materials was obtained, which could not be rehydrated.