The intercalation of formamide, potassium acetate, and hydrazine by halloysite and/or ka-olinite-rich samples, with and without subsequent displacement of the interlayer species by water or glycerol/water, has been investigated. Halloysite, as such, or in mixtures with kaolinite is completely expanded by all the treatments used, thereby enabling halloysite concentrations to be determined from the basal X-ray powder diffraction (XRD) peak ratios of the appropriate complexes. The values so obtained are usually proportional to the abundance of tubes, laths, and spherules in the transmission electron micrographs of the samples. The analysis of kaolin samples (halloysite plus kaolinite) by intercalation methods is less straight forward because a proportion of the kaolinite component in the system may not expand, even after lengthy (≥ 18 days) contact of the sample with the intercalating agent. Only prolonged immersion in hydrazine produces complete or nearly complete expansion of this component. When allowance is made for the presence of non-clay mineral components, kaolin-mineral percentages estimated from XRD peak intensity ratios of the hydrazine complexes generally agree with values derived from differential thermal analysis to within ±10%. Kaolinite in mixtures with halloysite cannot be directly determined by intercalation procedures inasmuch as treatments which result in complex formation with kaolinite also expand halloysite. In such systems, kaolinite can be estimated by difference between the concentration of kaolin minerals and halloysite.

Factors influencing the degree of intercalation (‘reactivity’) of kaolinite group minerals have been investigated using six kaolin minerals, with variable crystallinity and particle size. Tests were performed to measure the degree of intercalation with potassium acetate, formamide, dimethylsulphoxide and hydrazine.

These experiments indicate that intercalation degree depends on a number of factors, including particle size, degree of ordering, type of guest molecules, method of intercalation, and presence and types of impurities. Anew method for determination of the degree of intercalation is proposed, which is not dependent on the intensity of complex reflections. The results indicate that formamide is the most sensitive reagent to distinguish differently ordered kaolin minerals whereas hydrazine appears as the most appropriate reagent to differentiate kaolin minerals from other 7 Å phases.

Kaolinite- and halloysite-potassium acetate complexes were synthesized by cogrinding with solid potassium acetate (mechanochemical intercalation). The efficiency of mechanochemical intercalation was compared to the intercalation in solution and by homogenization. The effects of ageing and grinding parameters (grinding time, sample:grinding body mass ratio (SGMR), rotational speed) and the humidity on the intercalation were studied. The degree of intercalation increased exponentially with ageing of the samples prepared by mechanochemical and homogenization techniques. For the mechanochemical and homogenization techniques the required amount of potassium acetate per gram of kaolin (∼0.4 g/g) was two orders of magnitude lower than that for the solution intercalation (78.6 g/g). The highest degree of intercalation (86%) and the lowest structural deformation were achieved by the mechanochemical method (¼ h of co-grinding with 1:2 SGMR at 300 rpm), followed by 16 h ageing at 57% relative humidity.