The present paper reports a novel synthetic procedure of both calcium ferrites (CaFe 2O 4 and Ca 2Fe 2O 5) starting from mechanically activated mixtures of organic precursors (calcium citrate tetrahydrate and iron(III) oxalate hexahydrate). With the help of TG analysis the different stages of the mass loss process taking place could be individuated and their chemical nature assessed. The DSC signal, recorded on the same sample, revealed that much higher enthalpies are released from the milled mixtures than those expected on the basis of the reactions taking place. From such enthalpic excess the enthalpies of formation of Ca 2Fe 2O 5 and CaFe 2O 4 have been obtained. X-ray powder diffraction (XRPD) indicated that the mechanically activated mixtures yield, after an 18 h-annealing at 800 °C (or 750 °C), Ca 2Fe 2O 5 (or CaFe 2O 4). On the contrary, the same compounds could be obtained, when starting from physical mixtures, only by performing thermal treatments (for t > 18 h) at 1180 °C (Ca 2Fe 2O 5) or 1100 °C (CaFe 2O 4).
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