Praseodymium Zircon Yellow

Abstract

The properties of praseodymium zircon yellow and of corresponding samples with a nominal substitution of Ce4+ for Zr4+ as well as Ti4+ for Si4+ (system ZrSiO,: Pr,Ce,Ti,) are investigated by X-ray methods, diffuse reflectance, and vibrational spectroscopy. From the present results follows that the ZrSiO, structure does not tolerate a significant substitution level on either Zr4+ or Si4+ regular lattice positions by the larger foreign ions Ce4+, Pr4+, and Ti4+. Thus, the yellow colour is the result of the usual colour-centre formation, charge compensated by Pr3 + ; whereas the highly forbidden 4f -+. 4f transitions of Pr3+ are practically without influence on the coloration. Die Eigenschaften von Zirkon-Praseodym-Gelb sowie von entsprechenden Proben mit einer nominellenSubstitution von Ce4+ fur Zr4+ bzw. Ti4+ fur Si4+ (System ZrSiO,: Pr,Ce,Ti,) werden mit rontgenographischen Methoden sowie durch diffuse Reflexionsspektroskopie und Schwingungsspektroskopie untersucht. Die erzielten Ergebnisse zeigen, daB die Zirkon-Struktur weder einen bedeutenden Substitutionsgrad auf regullren Zr4+-noch auf Si4+-P1atzen durch die groBeren Ionen Ce4+, Pr4+ oder Ti4+ zulal3t. Daher ist die gelbe Farbe das Resultat einer gewohnlichen Farbzentren-Bildung, der Ladungsausgleich erfolgt durch Pr3 +. Dagegen uben die stark verbotenen 4f + 4f-Ubergange von Pr3 + praktisch keinen EinfluR auf die Farbung aus.

Blue Zircon from Ratanakiri, Cambodia

“…It should be added that doped synthetic ZrSiO 4 of various colouration is used as high-temperature stable and chemically inert pigments. These include, for instance, yellow Pr 3+ -doped ZrSiO 4 (Stiebler et al, 1992;Del Nero et al, 2004), 'lemon'-yellow Tb 3+ -doped ZrSiO 4 (Kar et al, 2004), blue V 4+ -doped ZrSiO 4 (Demiray et al, 1970;Niesert et al, 2002;Pyon et al, 2011) and pink-to-red Fe-doped ZrSiO 4 (Cappelletti et al, 2005). It is, however, well known that the colours of natural zircon have different causes than those of the synthetic pigments, the latter of which contain dopant levels several orders of magnitude above the concentrations of the same elements in natural zircon.…”

Synthesis and characterization of (Pr, Ce)‐ZrSiO4 ceramic pigments: The properties of the pigments and the effect of Ce

“…Fujii et al first reported the existence of Pr‐doped zircon pigment in 1952. The mechanism underlying the formation of Pr‐ZrSiO 4 , the locations of Pr, as well as its valence states, and the types and uses of mineralizer have been studied in detail by many researchers. The reported methods of synthesis for Pr‐ZrSiO 4 pigment include solid‐state reaction, sol‐gel, nonhydrolytic sol‐gel and hydrothermal methods .…”

The Electron Paramagnetic Resonance of Fe3+ Observed in Two Axial Sites in Synthetic Single Crystals of Zircon (ZrSiO4)

“…[1,2] and references therein) and of the colour of zircon crystals and powders [3,4]. These studies contributed to the understanding of these materials for their possible use as lasers and television phosphors (see Refs.…”

“…These studies contributed to the understanding of these materials for their possible use as lasers and television phosphors (see Refs. Some of these ions together with Fe 3+ are used in the manufacture of pigments (V 4+ , blue, Pr 3+ , yellow [4,6] and Fe 3+ , pink [3]). Much less has been published on the spectra of 3d ions in these systems.…”