Mechanism of Reduction-Nitridation of Synthetic Kaolinite in the Presence of Carbon.

"Carbothermic reduction and nitridation reactions using synthetic kaolinite mineral were investigated for the formation of silicon based nitrogen ceramics. The temperature dependence of the reaction rate and its effect on phases formed are reported. The effect of the reactivity of carbon on the kinetics of formation of AIN and ShN4 is discussed. Using the standard Gibbs free energy values for the formation of nitrides and oxides of aluminium and silicon, a log po2 verses I/T diagram is constructed. The experimental data results are discussed and compared with the predicted phase equilibria. We also report the influence of sub-oxide gaseous species on the microstructure of the ceramic phases produced.IntroductionSynthetic kaolinite is a clay containing alumina, silica and water of crystallisation, and has a chemical formula 3(Al2O 3.2SiO2.2H2O). This mineral is relatively inexpensive and, is therefore an ideal candidate for use in the production of ceramic powder mixtures for example silicon nitride and aluminium nitride for composite material formation, When the mineral is heated, the water of crystallisation from the crystal lattice is lost via the 3(Al2O 3.2SiO2.2H2O) = 3(Al2O3.2SiO2) + 6H2O reaction. It has been shown [1·2j that on further heating to 1673K, the anhydrous kaolinite decomposes to a mixture of mulllte and silica, 3(Al2O3.2SiO2) = 3Al2O 3.2SiO2 + 4SiO2 which is consistent with the alumina-silica phase diagram, shown in figure 1.The binary alumina-silica phase diagram has a well-defined sub-eutectic immiscibility dome and this characteristic dernixing behaviour is reflected in the thermal decomposition of anhydrous kaolinite consequently the microstructural features resemble the spinodal decomposition process. It is well established that the spinodal decomposition process raises the nucleation frequency due to their low free energy barrier, (?G). The small magnitude of this barrier consequently promotes the evolution of a very fine microstructure. The process of spinodal decomposition is therefore expected to be influential during the reduction-nitridation of kaolinite minerals."