Kaolin-group clay minerals can be modified to form nanotubular and mesoporous structures with interesting catalytic properties, but knowledge of the best methods for preparing these structures is still incomplete. The objective of this study was to investigate intercalation/deintercalation as a method for the delamination and rolling of kaolinite layers in relation to structural order. To prepare nanotubular material, kaolinites of different crystallinities and halloysite (all from Polish deposits) were chosen. The experimental procedure consisted of four stages: (1) preparation of a dimethyl sulfoxide precursor intercalate; (2) interlayer grafting with 1,3-butanediol; (3) hexylamine intercalation; and (4) deintercalation of amine-intercalated minerals using toluene as the solvent. Structural perturbations and changes in the morphology of the minerals were examined by X-ray diffraction, Fourier transform infrared spectroscopy, differential scanning calorimetry, and transmission electron microscopy (TEM). The number of rolled kaolinite layers depended heavily on the efficiency of the intercalation steps. An increase in the structural disorder and extensive delamination of the minerals subjected to chemical treatment were recorded. Kaolinite particles which exhibited tubular morphology or showed rolling effects were observed using TEM. The nanotubes formed were ∼30 nm in diameter, with their length depending on the particle sizes of the minerals.

In this study, a series of synthetic ferrihydrite samples of Si/Fe molar ratios ranging from zero to 1.5 were heated up to 1000°C using simultaneous TG-DTA equipment. The XRD, FTIR, SEM-EDS and magnetic susceptibility measurements were carried out prior to and after heating. It has been found that silicate retards ferrihydrite transformation to hematite and affects crystallinity of the product. Low Si admixture in the precursor reduces hematite crystal size severely, but the increase in average crystal dimensions with increasing Si/Fe molar ratio was observed. High Si content results in the formation of hematite which exhibits a wide range of crystal habits. The conversion of pure ferrihydrite to hematite proceeds without any intermediate phase, whereas the increasing silicate content in the pristine oxyhydroxide strongly affects the transformation pathway. During annealing of high-Si ferrihydrites, the presence of two or three intermediate Fe 2 O 3 polymorphs (gamma, epsilon and beta) was demonstrated prior to the crystallization of final a-Fe 2 O 3 . The conditions favoring crystallization of intermediate phases result from progressive silica polymerization which forms separate matrix-type phase and impedes the aggregation of iron oxide nanoparticles.

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