Characterization of kaolinite in the hardsetting clay fraction using atomic force microscopy, X-ray diffraction, and the Rietveld method

Purpose Brazilian soils that present extremely hard sub-superficial horizons when dry and friable when humid are similar to the Australian and South African hardsetting horizons whose hardness can be mainly related to low crystallinity. Studies involving refinement by the Rietveld method with X-ray diffraction (RM-XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), and their relation have not been carried out in hardsetting horizon soils. Thus, the objective of this study is to obtain information about the kaolinite in the hardsetting horizon of a Yellow Argisol clay fraction, taking into consideration the results of isomorphic substitution, crystallite average size, and microstrains, relating them to particle image analysis regarding their morphology and size. Materials and methods Soil samples were collected in the hardsetting horizon of a Yellow Argisol in the Coastal Tablelands region, which covers the whole Brazilian Northeast coast and part of the Southeast region. The sample was powdered, sieved, and submitted to dispersion and physical fractioning process by sedimentation. The clay fraction was analyzed by RM-XRD, AFM, and SEM techniques. Results and discussion The RM-XRD provided improvement of indices with isomorphic substitutions in the goethite [Fe 0.70 Al 0.30 O(OH)], kaolinite [Al 1.44 Fe 0.56 Si 2 O 5 (OH) 4 ], and halloysite [Al 1.42 Fe 0.58 Si 2 O 5 (OH) 4 ]; 29 nm crystallite average size; 5 × 10 −3 microstrain; and 49.5% kaolinite. AFM analyses indicated particle average size from 80 to 250 nm and average height from 60 to 80 nm. By relating this data, it was possible to estimate that the particles under analysis are kaolinite composed of 3 to 9 crystallites and stacking of 88 to 112 layers. Conclusions The process, analyses, and comparisons such as crystallographic and morphologic information about the kaolinite mineral particles contribute to the comprehension of the hardsetting horizon soil nature as well as other soils that present minerals with a high degree of isomorphic substitution.