Ordering kinetics in synthetic Mg(Al,Fe3+)2O4 spinels: Quantitative elucidation of the whole Al-Mg-Fe partitioning, rate constants, activation energies
A novel procedure, based on the application of the kinetics simulator Gepasi, has been successfully applied for modeling the cation ordering process in two synthetic Mg(Al2-yFe3+y)O4 spinels (y~ 0.39 and 0.54, samples F39 and F54, respectively). The kinetic profiles suggested a two-stage mechanism, with rapid inter-site exchange of Fe3+ with Mg followed by slow exchange of Al with Mg. The trial to apply the classical approaches, based on the explicit solutions of the differential equations corresponding to single-cation (Sha-Chappel model) or two-cation (Müller model) exchange reactions, proved not feasible in the whole time range, thus implying a lack of information about the exchange proc…
Synthetic and natural chromium bearing spinels: an optical spectroscopy study
Four samples of synthetic chromium-bearing spinels of (Mg, Fe2+)(Cr, Fe3+)2O4 composition and four samples of natural spinels of predominantly (Mg, Fe2+)(Al, Cr)2O4 composition were studied at ambient conditions by means of optical absorption spectroscopy. Synthetic end-member MgCr2O4 spinel was also studied at pressures up to ca. 10 GPa. In both synthetic and natural samples, chromium is present predominantly as octahedral Cr3+ seen in the spectra as two broad intense absorption bands in the visible range caused by the electronic spin-allowed 4A2g → 4T2g and 4A2g → 4T1g transitions (U- and Y-band, respectively). A distinct doublet structure of the Y-band in both synthetic and natural spine…
A Raman spectroscopy study of the oxidation processes in synthetic chromite FeCr2O4
Abstract A crystal of synthetic chromite FeCr2O4 has been annealed in air at 700 °C for 50 days at room pressure in order to study physical-chemical changes. After the annealing treatment, Scanning Electron Microscopy (SEM) images of the polished surface of the sample showed areas of different composition. Detailed Raman mapping revealed that the annealed chromite undergoes an oxidation process, proceeding inwards from the outer surface and leading to the transformation of chromite to magnetite, and ultimately to hematite. The oxidation process also leads to the formation of trellis-like lines, arguably via stress-related mechanisms associated with the phase transformation and consequent vo…