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Title: High-performance yellow ceramic pigments Zr(Ti{sub 1-x-y}Sn {sub x-y}V {sub y}M {sub y})O{sub 4} (M = Al, In, Y): Crystal structure, colouring mechanism and technological properties

Abstract

Zirconium titanate-stannate doped with V with co-dopants Al, In or Y was synthesised by solid state reaction and its structural (XRD, SEM), optical (DRS) and technological properties were determined to assess its potential use as ceramic pigment. These compounds have a srilankite-type, disordered orthorhombic structure, implying a random distribution of Zr, Ti, Sn and dopants in a single, strongly distorted octahedral site. Doping caused an increase of unit-cell dimensions, metal-oxygen distances and octahedron distortion. Optical spectra show crystal field electronic transitions of V{sup 4+} as well as intense bands in the blue-UV range due to V{sup 4+}-V{sup 5+} intervalence charge transfer and/or to V-O charge transfer. The formation of oxygen vacancies is supposed to compensate the occurrence of V{sup 4+} ensuring the lattice charge neutrality. These srilankite-type oxides develop a deep and brilliant yellow shade with colourimetric parameters close to those of industrial ceramic pigments. Technological tests in several ceramic applications proved that zirconium titanate-stannate is very stable at high temperature, exhibiting an excellent performance in the 1200-1250 deg. C range, even better than praseodymium-doped zircon.

Authors:
 [1];  [2];  [1];  [3]
  1. ISTEC-CNR, Institute of Science and Technology for Ceramics, Via Granarolo 64, 48018 Faenza (Italy)
  2. ISTEC-CNR, Institute of Science and Technology for Ceramics, Via Granarolo 64, 48018 Faenza (Italy). E-mail: matteucci@istec.cnr.it
  3. Department of Earth Sciences, University of Ferrara, Via Saragat 1, 44100 Ferrara (Italy)
Publication Date:
OSTI Identifier:
20900946
Resource Type:
Journal Article
Resource Relation:
Journal Name: Materials Research Bulletin; Journal Volume: 42; Journal Issue: 1; Other Information: DOI: 10.1016/j.materresbull.2006.05.014; PII: S0025-5408(06)00207-8; Copyright (c) 2006 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; CERAMICS; CRYSTAL FIELD; DOPED MATERIALS; OPTICAL PROPERTIES; ORTHORHOMBIC LATTICES; OXIDES; PIGMENTS; PRASEODYMIUM; SCANNING ELECTRON MICROSCOPY; TITANATES; VACANCIES; VANADIUM IONS; X-RAY DIFFRACTION; ZIRCON; ZIRCONIUM

Citation Formats

Dondi, Michele, Matteucci, Francesco, Zama, Isabella, and Cruciani, Giuseppe. High-performance yellow ceramic pigments Zr(Ti{sub 1-x-y}Sn {sub x-y}V {sub y}M {sub y})O{sub 4} (M = Al, In, Y): Crystal structure, colouring mechanism and technological properties. United States: N. p., 2007. Web. doi:10.1016/j.materresbull.2006.05.014.
Dondi, Michele, Matteucci, Francesco, Zama, Isabella, & Cruciani, Giuseppe. High-performance yellow ceramic pigments Zr(Ti{sub 1-x-y}Sn {sub x-y}V {sub y}M {sub y})O{sub 4} (M = Al, In, Y): Crystal structure, colouring mechanism and technological properties. United States. doi:10.1016/j.materresbull.2006.05.014.
Dondi, Michele, Matteucci, Francesco, Zama, Isabella, and Cruciani, Giuseppe. Thu . "High-performance yellow ceramic pigments Zr(Ti{sub 1-x-y}Sn {sub x-y}V {sub y}M {sub y})O{sub 4} (M = Al, In, Y): Crystal structure, colouring mechanism and technological properties". United States. doi:10.1016/j.materresbull.2006.05.014.
@article{osti_20900946,
title = {High-performance yellow ceramic pigments Zr(Ti{sub 1-x-y}Sn {sub x-y}V {sub y}M {sub y})O{sub 4} (M = Al, In, Y): Crystal structure, colouring mechanism and technological properties},
author = {Dondi, Michele and Matteucci, Francesco and Zama, Isabella and Cruciani, Giuseppe},
abstractNote = {Zirconium titanate-stannate doped with V with co-dopants Al, In or Y was synthesised by solid state reaction and its structural (XRD, SEM), optical (DRS) and technological properties were determined to assess its potential use as ceramic pigment. These compounds have a srilankite-type, disordered orthorhombic structure, implying a random distribution of Zr, Ti, Sn and dopants in a single, strongly distorted octahedral site. Doping caused an increase of unit-cell dimensions, metal-oxygen distances and octahedron distortion. Optical spectra show crystal field electronic transitions of V{sup 4+} as well as intense bands in the blue-UV range due to V{sup 4+}-V{sup 5+} intervalence charge transfer and/or to V-O charge transfer. The formation of oxygen vacancies is supposed to compensate the occurrence of V{sup 4+} ensuring the lattice charge neutrality. These srilankite-type oxides develop a deep and brilliant yellow shade with colourimetric parameters close to those of industrial ceramic pigments. Technological tests in several ceramic applications proved that zirconium titanate-stannate is very stable at high temperature, exhibiting an excellent performance in the 1200-1250 deg. C range, even better than praseodymium-doped zircon.},
doi = {10.1016/j.materresbull.2006.05.014},
journal = {Materials Research Bulletin},
number = 1,
volume = 42,
place = {United States},
year = {Thu Jan 18 00:00:00 EST 2007},
month = {Thu Jan 18 00:00:00 EST 2007}
}
  • Synthetic hollandite compounds of composition Ba/sub x/M(IV)/sub 4-2x/N(III)/sub 2x/O/sub 8/ (M=Ti, Ge, Ru, Zr, Sn; N=Al, Sc, Cr, Ga, Ru, In) and Sr/sub x/M(IV)/sub 4-2x/N(III)/sub 2x/O/sub 8/ (M=Ti, Ge, Ru; N=Al, Cr, Ga) and (A, Ba)/sub x/Ti/sub y/Al/sub z/O/sub 8/ with A=Rb, Cs, Ca, Sr have been studied by electron and X-ray diffraction and high resolution electron microscopy. They have been found to be stable only within certain ranges of x, depending on the M and N ions. The lower value of x is never less than 0.56, the upper x level is about 0.73. Higher x are correlated withmore » larger radii of M and N. The variation in x gives rise to an incommensurate occupation by the A ions in the tunnels. Correlation among tunnel sequences varies widely, also depending on the nature of the M and N ions. The lower and upper x, the cell dimensions, the correlation between the tunnels and the stability in water at 300/sup 0/C of the existing hollandites are given.« less
  • The [M{sub x}{sup II}M{sub 2.5-x}{sup III}(H{sub 2}O){sub 2}(HP{sup III}O{sub 3}){sub y}(P{sup V}O{sub 4}){sub 2-y}F; M=Fe (1), x=2.08, y=1.58; M=Co (2), x=2.5, y=2; Ni (3), x=2.5, y=2] compounds have been synthesized using mild hydrothermal conditions at 170 deg. C during five days. Single-crystals of (1) and (2), and polycrystalline sample of (3) were obtained. These isostructural compounds crystallize in the orthorhombic system, space group Aba2, with a=9.9598(2), b=18.8149(4) and c=8.5751(2) A for (1), a=9.9142(7), b=18.570(1) and c=8.4920(5) A for (2) and a=9.8038(2), b=18.2453(2) and c=8.4106(1) A for (3), with Z=8 in the three phases. An X-ray diffraction study reveals that themore » crystal structure is composed of a three-dimensional skeleton formed by [MO{sub 5}F] and [MO{sub 4}F{sub 2}] (M=Fe, Co and Ni) octahedra and [HPO{sub 3}] tetrahedra, partially substituted by [PO{sub 4}] tetrahedra in phase (1). The IR spectra show the vibrational modes of the water molecules and those of the (HPO{sub 3}){sup 2-} tetrahedral oxoanions. The thermal study indicates that the limit of thermal stability of these phases is 195 deg. C for (1) and 315 deg. C for (2) and (3). The electronic absorption spectroscopy shows the characteristic bands of the Fe(II), Co(II) and Ni(II) high-spin cations in slightly distorted octahedral geometry. Magnetic measurements indicate the existence of global antiferromagnetic interactions between the metallic centers with a ferromagnetic transition in the three compounds at 28, 14 and 21 K for (1), (2) and (3), respectively. Compound (1) exhibits a hysteresis loop with remnant magnetization and coercive field values of 0.72 emu/mol and 880 Oe, respectively. - Abstract: Polyhedral view of the crystal structure of the [M{sub x}{sup II}M{sub 2.5-x}{sup III}(H{sub 2}O){sub 2}(HP{sup III}O{sub 3}){sub y}(P{sup IV}O{sub 4}){sub 2-y}F; M=Fe, x=2.08, y=1.58; M=Co, Ni, x=2.5, y=2] compounds showing the sheets along the [001] direction.« less
  • Karrooite, MgTi{sub 2}O{sub 5}, is a promising ceramic pigment due to its high refractoriness and refractive indices, as well as its ability to host transition metal ions in two crystallographically distinct octahedral sites. The colouring performance was investigated combining X-ray powder diffraction with UV-vis-NIR spectroscopy on karrooite doped with V, Cr, Mn, Fe, Co or Ni (M) according to the formula Mg{sub 1-x}Ti{sub 2-x}M{sub 2x}O{sub 5}, with x=0.02 and 0.05. Transition metals solubility in the karrooite lattice is not complete and a second phase is always present (geikielite or rutile). Structural data proved that incorporation of different chromophore ions intomore » the karrooite structure affects unit cell parameters, bond length distances and angles, site occupancies and therefore cation order-disorder. Optical spectra exhibit broad absorbance bands of Co(II), Cr(IV), Fe(III), Mn(II), Mn(III), Ni(II), V(IV) with distinct contributions by cations in the M{sub 1} and M{sub 2} sites. Karrooite pigments have colours ranging from orange to brown-tan (Cr, Fe, Mn, V) to green (Co) and yellow (Ni) that are stable in low-temperature (<1050 deg. C) ceramic glazes and glassy coatings. - Graphical abstract: Karrooite is a promising ceramic pigment for high refractoriness and refractive indices. Incorporation of V(IV), Cr(IV), Mn(II)+Mn(III), Fe(III), Co(II) or Ni(II) in two crystallographically distinct octahedral sites affects unit cell parameters, bond length distances and cation order-disorder, leading also to distinct optical bands from the two different sites, so reducing colour purity.« less
  • New substituted copper titanates with the CaCu/sub 3/Ti/sub 4/O/sub 12/ perovskite-like structure were synthesized and characterized. Their formula is Li absolute value of Cu/sub 3-x/Li/sub x/ absolute value of Ti/sub 3-x/M/sub 1 + x//sup V/ O/sub 12/. There is a homogeneity range for M/sup V/ = Nb, 0.12 less than or equal to x less than or equal to 0.33, and a unique composition for M/sup V/ = Ta, x = 0.33. The unit cell is cubic: a approx. 2a/sub p/ (parameter of the ideal cubic cell) approx. 7.40 A. The CaCu/sub 3/Ti/sub 4/O/sub 12/-type structure was confirmed from anmore » X-ray powder structural determination. Lithium occupies both square planar sites where it replaces copper and icosahedral sites, with a probable delocalization. Crystal chemistry of the AC/sub 3/B/sub 4/O/sub 12/ structure is considered, taking into account the evolution of anion packing and the distortion of polyhedra. A diagrammatic representation is proposed so that precise information on the regularity of the C/sub 3/B/sub 4/O/sub 12/ network can be obtained.« less
  • An alcoholysis exchange between tris(hydroxymethyl)ethane (THME-H{sub 3}) or tris(hydroxymethyl)propane (THMP-H{sub 3}) and group IV metal isopropoxides yields compounds of the general formula (THMR){sub 2}M{sub 4}(OCHMe{sub 2}){sub 10}[M = Ti (R = E, 1; P, 2); Zr (R = E, 3; P, 4)]. 1 and 2 are formed in toluene, at ambient glovebox temperatures, and adopt a typical fused-M{sub 3}O{sub 12} structure where each titanium atom is surrounded by six oxygens in a slightly distorted face-shared bioctahedral arrangement. All of the oxygens of the central core are from the THMR ligand, present as {mu}-O and {mu}{sub 3}-O oxygen bridges. Generation ofmore » 3 or 4 requires heating in toluene at reflux temperatures. The zirconium atoms of 3 possess an extremely distorted edge-shared bioctahedral geometry where the central core consists of a Zr{sub 4}O{sub 8} ring (eight oxygens: six from THME ligands and two from isopropoxide ligands). Each of the zirconium atoms is six-coordinated with four bridging oxygens and two terminal isopropoxide ligands. Spincast deposited films generated from toluene solutions of 1 and 3 indicate that increased uniformity of the films and decreased hydrolysis occur in comparison to the cases of Ti(OCHMe{sub 2}){sub 4}, 5, and [Zr(OCHMe{sub 2}){sub 4}{center_dot}HOCHMe{sub 2}]{sub 2}, 6, respectively.« less