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Kinetic study of the kaolinite-mullite reaction sequence. Part II: Mullite formation


The present work is a follow-up of the investigation on the decomposition reaction of kaolinite as a function of the defectivity of the starting material and the temperature of reaction. In the present work we study the high temperature reaction of mullite synthesis from kaolinite, from the starting point of the results obtained in the first part.

Time resolved energy-dispersive powder diffraction patterns have been measured using synchrotron radiation in isothermal conditions. The apparent activation energy for mullite nucleation and growth is found to be related to the defective structure of the starting kaolinite, which thus must have an influence on the chemical homogeneity of the amorphous intermediate phase.

The analysis of the kinetic data indicate that the initial reaction mechanism is controlled by mullite nucleation, while as the reaction proceeds it shifts towards a grain growth-limited process which is intermediate between phase boundary and diffusion controlled. The order of the reaction obtained from standard analysis of the isothermal kinetic data is lower in the case of the ordered kaolinite KGa-1, in agreement with a rate limiting process more strongly limited by diffusion.

For each sample there is a small but significant decrease in the order of the reaction at higher temperature: we interpret the change as related to the variation of the diffusion process in the amorphous phase due to the growing grains of mullite and cristobalite.

The values of the activation energies and induction times are comparable neither to a model of mullite formation from a monophasic gel, nor mullite formation from a diphasic gel, being intermediate between the two. We can infer that the amorphous precursors from natural kaolinites can be considered pseudo-monophasic gel-like phases, approaching the monophasic gel-like behaviour as the defectivity of the initial kaolinite increases.

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Correspondence to A. Gualtieri.

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Gualtieri, A., Bellotto, M., Artioli, G. et al. Kinetic study of the kaolinite-mullite reaction sequence. Part II: Mullite formation. Phys Chem Minerals 22, 215–222 (1995). https://doi.org/10.1007/BF00202254

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  • Kaolinite
  • Apparent Activation Energy
  • Induction Time
  • Cristobalite
  • Defective Structure