Abstract
Zirconia oxynitride rare-earth-doped pigments were prepared by ammonolysis of the zirconium rare-earth oxides, previously synthesized using the citrate complexation/calcination route. Different coloration has been obtained, the intensity of which is a function of the nitrogen amount in the case of the oxynitrides; in the case of the oxides, both color and intensity depend on the doping amount of rare earth. The obtained phases, Zr(1−x)CexO2, Zr(1−x)RxO(2−x/2)□x/2, with R = Eu or Er and Zr(1−x)RxO(2−x/2−3/2y)Ny□x/2■y/2 (R = Ce, Eu, and Er), have been characterized by x-ray powder diffraction, scanning electron microscopy, and reflectance spectra data. These results show that the phases with minor rare-earth concentration adopt a baddeleyite-type structure, with a monoclinic symmetry, space group P21/c. By increasing the rare-earth doping, the obtained phases crystallize with the fluorite structure with tetragonal (P42/nmc) or cubic symmetry (Fm-3m). On the other hand, the study of the magnetic properties of the oxides and oxynitrides indicate a paramagnetic behavior, and in the case of the cerium oxide, the nitridation process produces the reduction from Ce4+ to Ce3+. Diffuse reflectance data and CIE-LAB color coordinates suggest that these ceramics based on nitrogen containing zirconia are expected to be promising candidates as new ecological inorganic pigments.
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References
Industrial Inorganics Pigments, edited by G. Buxhaum (VCH, Weinheim Germany, 1993).
B. Gonzalo, J. Romero, F. Fernandez, M.J. Torralvo: (Bi,R)2O3 (R: Nd, Sm and Dy) oxides as potencial pigments. J. Alloys Compd. 323–324, 372 (2001).
R. Olazcuaya, G. Le Polles, A. El. Kira, G. Flem Le, P. Maestro: Optical properties of Ce1-xPrx O2 powders and their applications to the coloring ceramics. J. Solid State Chem. 71, 570 (1987).
V. Sanchez, LopèE.F. z, M. Panizza: Characterization of cubic ceria-zirconia powders by x-ray diffraction and vibrational and electronic spectroscopy. Solid State Sci. 5, 1369 (2003).
M. Kakihana, S. Kato, M. Yashima, M. Yoshimura: Preparation of tetragonal ZrO2–12 mol% CeO2 and ZrO2–6 mol% YO1.5 solid solutions at reduced temperature by a simple aqueous solution route using citrid acid as a complexant. J. Alloys Compd. 280, 125 (1998).
Y.B. Cheng, D.P. Thompson: Nitrigen-containing tetragonal zirconia. J. Am. Ceram. Soc. 74, 1135 (1991).
Y.B. Cheng, D.P. Thompson: Role of anion vacancies in nitrogen-stabilized zirconia. J. Am. Ceram. Soc. 76, 683 (1993).
M. Lerch: Nitridation of zirconia. J. Am. Ceram. Soc. 79, 2641 (1996).
S.J. Clarke, C.W. Michie, M.J. Rosseinsky: Structure of Zr2ON2 by neutron powder diffraction: The absence of nitride-oxide ordering. J. Solid State Chem. 146, 399 (1999).
M. Lerch, J. Wrba, J. Lerch: Synthesis and characterization of oxynitrides in the ZrO2-rich part of the systems Ca–Zr–O–N and Mg–Zr–O–N. J. Solid State Chem. 128, 282 (1997).
J. Wrba, M. Lerch: Phase relationships in the ZrO2-rich part of the systems Y–Zr–N–O, Ca–Zr–N–O, and Mg–Zr–N–O up to temperatures of 1150 °C. J. Eur. Ceram. Soc. 18, 1787 (1998).
J. Wendel, M. Lerch, W. Laqua: Novel zirconia-based superionic conductors: The electrical conductivity of Y–Zr–O–N materials. J. Solid State Chem. 142, 163 (1999).
S. Gutzov, M. Lerch: Optical properties of europium containing zirconium oxynitrides. Opt. Mater. 24, 547 (2003).
S. Gutzov, M. Lerch: Preparation and optical properties of Zr–Ce–O–N materials. J. Eur. Ceram. Soc. 21, 595 (2001).
www.lecoinstrumentos.es.
J. Rodríguez-Carvajal: In Abstracts of the Satellite Meeting on Powder Diffraction of XVth Congress of the Int. Union of Crystallography Toulouse, (1990), p. 127.
R. Pastrana, J. Isasi, R. Sáez: Synthesis and characterization of inorganic pigments based on transition metal oxynitrides. J. Mater. Res. (in press).
E. de la Rosa-Cruz, L.A. Diaz-Torres, J. Rojas Rodriguez: Luminiscence and visible upconversion in nanocrystalline ZrO2:Er3+. Appl. Phys. Lett. 83, 4903 (2003).
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Pérez-Estébanez, M., Pastrana-Fábregas, R., Isasi-Marín, J. et al. Inorganic pigments based on fluorite-type oxynitrides. Journal of Materials Research 21, 1427–1433 (2006). https://doi.org/10.1557/jmr.2006.0177
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DOI: https://doi.org/10.1557/jmr.2006.0177