Abstract
Examining the kinetics of solids’ thermal decomposition with multiple overlapping steps is of growing interest in many fields, including materials science and engineering. Despite the difficulty of describing the kinetics for complex reaction processes constrained by physico-geometrical features, the kinetic deconvolution analysis (KDA) based on a cumulative kinetic equation is one practical method of obtaining the fundamental information needed to interpret detailed kinetic features. This article reports the application of KDA to thermal decomposition of clay minerals and indigo–clay mineral hybrid compounds, known as Maya blue, from ancient Mayan civilization. Maya blue samples were prepared by heating solid mixtures of indigo and clay minerals (palygorskite and sepiolite), followed by purification. The multistep thermal decomposition processes of the clay minerals and Maya blue samples were analyzed kinetically in a stepwise manner through preliminary kinetic analyses based on a conventional isoconversional method and mathematical peak deconvolution to finally attain the KDA. By comparing the results of KDA for the thermal decomposition processes of the clay minerals and the Maya blue samples, information about the thermal decomposition steps of the indigo incorporated into the Maya blue samples was extracted. The thermal stability of Maya blue samples was interpreted through the kinetic characterization of the extracted indigo decomposition steps.
Highlights
Thermal decomposition of inorganic solids is a complex heterogeneous reaction that is regulated by chemical kinetics and physio-geometrical constraints [1,2,3]
The additional four reaction steps that were observed for Maya blue (MB) samples are attributed to the thermal decomposition of the indigo incorporated into the clay mineral substrates
Discoloration of MB samples occurred during the second reaction step of the thermal decomposition of the indigo incorporated into the clay mineral substrates
Summary
Thermal decomposition of inorganic solids is a complex heterogeneous reaction that is regulated by chemical kinetics and physio-geometrical constraints [1,2,3]. Consecutive or concurrent reaction steps that originated from both chemical [4,5,6,7,8,9] and physio-geometrical reaction mechanisms can occur [10,11,12,13,14,15,16], wherein the individual reaction steps may be kinetically dependent on one another. In the heterogeneous system, the rigorous formalization of the kinetic equation for multistep reactions is not so easy because of the physico-geometrical constraints of each reaction step and these complex interactions [17].
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