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1 Estación Experimental del Zaidín, CSIC, Profesor Albareda 1, 18008 Granada, Spain
2 HydrASA, UMR 6532, CNRS University of Poitiers, 40 Av. du Recteur Pineau, 86022 Poitiers, France
3 GAMLab - Institute of Methodologies for Environmental Analyses - CNR 85050 Tito Scale (PZ), Italy
4 CRMC2-CNRS Campus de Luminy, Case 913 Marseille Cedex, France
* E-mail address of corresponding author: javier.huertas{at}eez.csic.es
Fe-rich kaolinites were synthesized at 225°C in distilled water from gels with different Fe/Al ratios (0.15, 0.25, 0.35) and with Si/(Al + Fe) = 2. X-ray diffraction patterns of the reaction products showed that kaolinite was the only long-range crystalline phase synthesized. Analytical electron microscopy analyses of individual particles and Fourier transform infrared spectra indicated that Fe3+ was isomorphously incorporated into the kaolinite octahedral sheet and that tetrahedral substitution did not occur. The Fe content hosted in the synthetic kaolinites was similar to that incorporated into its corresponding starting gel. The highest Fe content in the particles reached 30 mol.% of the octahedral occupancy. Increases in the b parameter are proportional to increases in Fe for Al substitution. The extent of isomorphic substitution of Al by Fe is the highest ever reported for both natural and synthetic samples. At the nano-scale, there is no evidence of discontinuity in the solid-solution between the Si2Al2O7 and Si2Al1,4Fe0.6O7 end-members, such as short-range disorder or clustering of Fe and Al in domains.
Key Words: Fe3+ substitution • Kaolinite • Solid-solution • Synthesis
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