Ceramic pigments based on the Cr-doped malayaite structure were synthesized by solid state reaction and characterized by optical spectroscopy and combined X-ray and neutron powder diffraction in order to elucidate the still unclear chromium substitution mechanisms. The results show that coloration is actually due to simultaneous occurrence of Cr4+ and Cr3+ ions in the crystal lattice. Spectroscopy data confirm that Cr4+ is replacing Sn4+ in the octahedral site and, in minor amount, Si4+ in the tetrahedral site. In addition, neutron powder diffraction data suggest that Cr3+ substitution for octahedral Sn4+ is charge balanced by the formation of oxygen vacancies with no preference over the different oxygen sites. Upon incorporation of Cr ion, the SnO6 octahedra exhibit an off-centre displacement of central cation which in turn induces a rearrangement of both the octahedral and tetrahedral coordination shells.

Malayaite ceramic pigments: A combined optical spectroscopy and neutron/X-ray diffraction study

CRUCIANI, Giuseppe;ARDIT, Matteo;
2009

Abstract

Ceramic pigments based on the Cr-doped malayaite structure were synthesized by solid state reaction and characterized by optical spectroscopy and combined X-ray and neutron powder diffraction in order to elucidate the still unclear chromium substitution mechanisms. The results show that coloration is actually due to simultaneous occurrence of Cr4+ and Cr3+ ions in the crystal lattice. Spectroscopy data confirm that Cr4+ is replacing Sn4+ in the octahedral site and, in minor amount, Si4+ in the tetrahedral site. In addition, neutron powder diffraction data suggest that Cr3+ substitution for octahedral Sn4+ is charge balanced by the formation of oxygen vacancies with no preference over the different oxygen sites. Upon incorporation of Cr ion, the SnO6 octahedra exhibit an off-centre displacement of central cation which in turn induces a rearrangement of both the octahedral and tetrahedral coordination shells.
Cruciani, Giuseppe; Dondi, M.; Ardit, Matteo; Lyubenova, T. S.; Carda, J. B.; Matteucci, F.; Costa, A. L.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11392/1378158
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