The kinetics of the thermal decomposition of the kaolin: dimethylsulfoxide (kaolin: DMSO) and the kaolin: N-methylformarnide (kaolin: NMF) intercalates have been reexamined. Two different sample sizes (2 mg and 8 mg) and grain-size distributions (<45 μm and 45–63 μm were investigated using isothermal and dynamic gravimetry in the temperature range 100°–200oC. All sample configurations for the kaolin: DMSO intercalate (2 mg, <45 μm; 2 mg, 45–63 μm; 8 mg, <45 μm; 8 mg, 45–63 μm) followed the rate law -ln(1 - α) = kt to a value for α, the reaction fraction complete, of.6, yielding activation energies and standard deviations at the 99% confidence level of 85.5 ± 3.79 and 71.75 ± 8.75 kJ/mole for the isothermal and dynamic runs, respectively. The kaolin: NMF intercalate (2 mg, <45 μm) also followed the same rate law for α <.8, with activation energies and standard deviations at the 99% confidence level of 89 ± 5.05 and 79.25 ± 6.47 kj/mole for the isothermal and dynamic studies, respectively. In solution the rate law -ln(1 - α) = kt is known as first-order kinetics, but here it appears to represent the non-instantaneous nucleation of uniformly sized particles, followed by the inward movement of a reaction interface.

Bulk and size-fractionated kaolinites from seven localities in Australia as well as the Clay Minerals Society Source Clays Georgia KGa-1 and KGa-2 have been studied by X-ray diffraction (XRD), laser scattering, and electron microscopy in order to understand the variation of particle characteristics across a range of environments and to correlate specific particle characteristics with intercalation behavior. All kaolinites have been intercalated with N-methyl (NMF) after pretreatment with hydrazine hydrate, and the relative efficiency of intercalation has been determined using XRD. Intercalate yields of kaolinite: NMF are consistently low for bulk samples that have a high proportion of small-sized particles (i.e., <0.5 µm) and for biphased kaolinites with a high percentage (>60%) of low-defect phase. In general, particle size appears to be a more significant controlling factor than defect distribution in determining the relative yield of kaolinite: NMF intercalate.