Elucidation of the thermo-kinetics of the thermal decomposition of cameroonian kaolin: mechanism, thermodynamic study and identification of its by-products

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Abstract
This work elucidates the thermo-kinetics of the thermal conversion of cameroonian kaolin to metakaolin as the main product. The thermokinetical parameters (activation energy Ea and pre-exponential factor A) for the kaolin conversion were calculated using model-free methods, i.e. the Kissinger–Akahira–Sunrose (KAS) and the Flynn–Wall–Ozawa (FWO) method, and differential methods (Kissinger and Ozawa) additionally including iterative procedures for KAS and FWO methods (KAS-Ir; FWO-Ir). The cameroonian kaolin was heat-treated using three different heating rates, i.e. 5, 20 and 40 K min−1, leading to metakaolin samples named MK-(5), MK-(20) and MK-(40). The TGA analysis showed a total mass loss of ∼12.5% in two steps related to the dehydration (step 1) and dehydroxylation (step 2). The Ea of the two steps were most accurately determined using the iterative procedures KAS-Ir and FWO-Ir. The average Ea values were 88.44/88.58 kJ mol−1 for step 1 and 261.85/261.91 kJ mol−1 for step 2, for the KAS-Ir and FWO-Ir models, respectively. The most probable mechanism function was determined by the multiple heating rate method (MHR) and the Coats-Redfern method. The kinetic analyses showed that the dehydroxylation of kaolin is controlled by a random nucleation and subsequent growth mechanism (G4) and a second order chemical reaction (F2). Thermodynamic parameters, namely the entropy ΔS≠, the enthalpy ΔH≠ and Gibbs free energy ΔG≠, were evaluated. The average values of ΔS≠, ΔH≠ and ΔG≠ using both the KAS-Ir and FWO-Ir models exhibited less than 5% deviation. The obtained metakaolin samples were characterized using X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and Fourier-transform infrared spectroscopy (FT-IR).
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  • Deutscher Akademischer Austauschdienst

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