Heterogeneous Nucleation of Superparamagnetic Phases in “Fe-Bearing Cordierite-Glasses

Abstract

ABSTRACTGlasses of stoichiometric cordierite composition Mg2(Al1−xFex)4Si5O18, containing very low iron contents (x=0.015 and 0.005) have been investigated by 57Fe Mössbauer spectroscopy. At higher Fe concentrations spinel exsolution has been observed in X-ray powder patterns. To allow Mössbauer spectroscopy at very low Fe-concentrations (<0.8 weight* Fe2O), starting materials were doped with 100% 57Fe. Glasses prepared in air at 1560°C were also oxidized In water saturated O2 stream. Glasses were crystallized to cordierite by heating In air at 1100 to 1400°C. 57Fe-Mössbauer spectra of all samples are governed by a doublet typical for Fe2+ in octahedral coordination (IS: 1.09–1.15, QS: 2.00–2.31 in MM/s relative to metallic iron). X-ray powder patterns exhibit no additional phases. But, the 295 K and 5 K Mössbauer spectra of treated and untreated glasses and of cordierltes exhibit broad lines, which have been fitted by applying internal magnetic hyperfine fields H of ca. 500 kG. These lines are attributed to heterogeneously nucleated, superparamagnetic (MgFe) (AlFe)2O4 spinels of complex compositions. From the calculated subspec-tra one may conclude that 35 to 65% of the total iron, depending on preparation conditions, is incorporated in the spinels.