HF2EPR spectroscopy of Fe(III) impurities in a blue hercynite-based pigment
Journal of the European Ceramic Society 26 (2006) 2301–2305
F. Di Benedetto a, G. Andreozzi b, G. Baldi c, A. Barzanti c, G.P. Bernardini d, V. Faso c, L.A. Pardi e, M. Romanelli f
a Museo di Storia Naturale, Università di Firenze, via G. La Pira, 4, I-50121, Firenze, Italy
b Dip. di Scienze della Terra, Università di Roma, “La Sapienza”, P.le A. Moro, 5, I-00185, Roma, Italy
c Lab. Ricerca Avanzata, Gruppo Colorobbia, Via Pietramarina, 123, I-50053, Sovigliana, Italy
d Dip. di Scienze della Terra, Università di Firenze, via G. La Pira, 4, I-50121, Firenze, Italy
e IPCF, CNR, via G. Moruzzi, 1, I-56124, Pisa, Italy
f Dip. di Chimica, Università di Firenze, via della Lastruccia, 3, I-50019, Sesto Fiorentino, Italy
The nature and the behavior of a paramagnetic Fe(III) impurity, occurring in a newcharge-transfer hercynite-based blue pigment and determined through conventional electron paramagnetic resonance (EPR) and Mossbauer spectroscopy, was investigated and ascertained through highfield high-frequency EPR (HF2EPR) spectroscopy. The blue hercynite-based pigment is biphasic, containing both hercynite and corundum.
The HF2EPR spectral features, together with their temperature dependence allowed to assess the intensity and the symmetry of the Fe(III) crystal field interactions. Numerical simulations were used to determine the relevant hamiltonian parameters. The final attribution of Fe(III) to the octahedral sites in corundum was achieved.
The presence of corundum was found to remove ferric iron, eventually formed during the synthesis, from hercynite. The dilution of Fe(III) in the Al2O3 phase results in a quenching of its coloring effects. As a consequence, corundum acts as a buffer during the synthesis, stabilizingthe pigment chromatic yield.
© 2005 Elsevier Ltd. All rights reserved.
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