摘要
<p id="p-1">Maghemite (γ-Fe2O3) is a ferrimagnetic Fe oxide commonly found in tropical and subtropical soils, especially in the topsoil where it is usually a product of burning. Isomorphic substitution (IS) of the Fe in maghemite by different metals (mainly Alp>3+p>) can modify its mineralogical and chemical attributes, and these modifications may be important to understanding the formation and properties of this mineral in soils and sediments. The objective of this work was to evaluate the crystallochemical alterations of synthetic, Al-substituted maghemites prepared by the precipitation of magnetites from alkaline aqueous media containing FeSO4·7H2O with increasing amounts of Al2(SO4)3·7H2O to obtain hypothetical Alp>3+p> for Fep>3+p> substitutions ranging from 0.0 to 40.0 mol %. The Al-substituted magnetites were washed and dried, and then heated to 250°C for 4 h to form yellowish red maghemites that were characterized by total chemical analysis, X-ray diffraction, specific surface area (SSA), mass-specific magnetic susceptibility, infrared spectroscopy, transmission electronic microscopy, and color. Increasing Alp>3+p> substitution to an experimental maximum of 15.9 mol % decreased both the a0 dimension of the cubic unit cell (a0 = 0.8339 − 396.157×10p>−6p> Al, rp>2p> = 0.99) and the mean crystallite dimension (MCD = 76.4 − 3.15Al, rp>2p> = 0.79) of the maghemites. With the decrease in MCD came a more yellowish color, an increase in SSA, and a decrease in crystallinity as measured through extraction of the samples with acid ammonium oxalate. The mass-specific magnetic susceptibility of the maghemites increased with Alp>3+p> substitution up to 5.3 mol % and then decreased with further replacement of Fe by Al. Solid-phase aluminum in excess of 16 mol % substitution appeared to occur as a separate, poorly crystalline phase that was X-ray amorphous. p>