High NIR Reflectance and Photocatalytic Ceramic Pigments Based on M-Doped Clinobisvanite BiVO4 (M = Ca, Cr) from Gels

Clinobisvanite (monoclinic scheelite BiVO4 , S.G.I2/b) has garnered interest as a wide-band semiconductor with photocatalyst activity, as a high NIR reflectance material for camouflage and cool pigments and as a photoanode for PEC application from seawater. BiVO4 exists in four polymorphs: orthorhombic, zircon-tetragonal, monoclinic, and scheelite-tetragonal structures. In these crystal structures, V is coordinated by four O atoms in tetrahedral coordination and each Bi is coordinated to eight O atoms from eight different VO4 tetrahedral units. The synthesis and characterization of doped bismuth vanadate with Ca and Cr are studied using gel methods (coprecipitated and citrate metal–organic gels), which are compared with the ceramic route by means of the UV–vis–NIR spectroscopy of diffuse reflectance studies, band gap measurement, photocatalytic activity on Orange II and its relation with the chemical crystallography analyzed by the XRD, SEM-EDX and TEM-SAD techniques. The preparation of bismuth vanadate-based materials doped with calcium or chromium with various functionalities is addressed (a) as pigments for paints and for glazes in the chrome samples, with a color gradation from turquoise to black, depending on whether the synthesis is by the conventional ceramic route or by means of citrate gels, respectively; (b) with high NIR reflectance values that make them suitable as fresh pigments, to refresh the walls or roofs of buildings colored with them; and (c) with photocatalytic activity

Photocatalysts in ceramics

Advanced oxidation processes (AOPs) are oxidation processes based on sufficient concentrations of hydroxyl radicals to degrade dissolved organic compounds present in water or those that are dispersed in air to mineral forms or at least toharmless organic compounds. It is a safe and clean technology and, in certain processes, solar radiation can be used as process initiator. Titanium oxide is currently the reference as photocatalytic material, given its high activity, relative stability, low cost, and low toxicity. In this study, the use of ‘ceramic’ photocatalysts (ceramic composites) in treatment processes for specific pollutants in urban environments (VOCs and NOx ) and waste waters (persistent, bioaccumulative and toxic (PBT) organic compounds) is analysed, as well as their use ‘in ceramics’ on glazed ceramic tiles as substrates for photocatalytic layers or photocatalytic glaze

Orthorhombic (Fe2TiO5)-monoclinic (Cr2TiO5) solid solution series: Synthesis by gel routes, coloring and NIR reflectivity evaluation

CrxFe2-xTiO5 compositions of the solid solutions series from pseudobrookite Fe2TiO5 to monoclinic Cr2TiO5 have been prepared by the ceramic route and gel methods. At 1400 °C, pseudobrookite crystallizes in the x = 0–0.4 range, both pseudobrookite and monoclinic Fe-Cr2TiO5 coexist at x = 0.5, while in the range x = 0.7–1.5 monoclinic Fe-Cr2TiO5 crystallizes. Powders were 5 wt% glazed within a double-firing frit and the composition with x = 0.1 fired at 1000 °C exhibits the best red color (L*a*b* = 43.2/18.8/12.5), showing an intense band at 520 nm in the UV–Vis–NIR absorption spectrum associated with Cr4+ in octahedral coordination. The unit cell volume of the pseudobrookite decreases smoothly with the chromium amount, associated with the entrance of Cr4+ replacing Ti4+, while the volume of the Fe-Cr2TiO5 unit cell increases with the entrance of Fe3+ replacing Cr3+. The use of flux agents, the compaction pressure and the gel methods increase the crystallization of pseudobrookite but do not improve the reddish color, which is associated with the concentration of Cr4+ in the pigment. The optimized pigment composition Cr0.1Fe1.9TiO5 also shows a high NIR reflectance (55% in powder, 54% in glazed sample)

Study of the photocatalytic activity and cool characteristics of a novel palette of pigments

Se han preparado por el método cerámico composiciones optimizadas de una cuatricromía CMYK más un pigmento verde, basados en el dopado de cobalto en celsiana (Ba0,9Co0,1)Al2Si2O8 (cian), de cromo en armalcolita (MgFe)(Cr0,2Ti2,8Fe)O10 (magenta), de níquel en geikielita (Mg0,5Ni0,5)TiO3 (amarillo), la perovskita CrNdO3 (verde) y la misma perovskita mineralizada con fluoruros alcalinotérreos (BaF2 y MgF2) (negro). Los pigmentos en polvo y los vidriados obtenidos con una frita convencional de bicocción (1.050 °C) se han caracterizado respecto de su rendimiento colorimétrico mediante el modelo CIEL*a*b*; su capacidad refrigerante (como cool pigment), mediante la medida del índice de reflexión solar SRI, y su capacidad fotocatalítica, mediante el test de degradación de Naranja II. Los resultados obtenidos se comparan con los obtenidos con pigmentos comerciales de la familia CMY del circón tomados como referencia. Los resultados indican una coloración intensa de los polvos y de las plaquetas vidriadas con valores L* inferiores a los pigmentos homólogos del circón, en cambio el chroma obtenido con los pigmentos del circón es superior (b* negativo para el cian, a* positivo para el magenta o b* positivo para el amarillo). Respecto a su capacidad refrigerante, los resultados indican valores SRI altos y superiores en el caso de la celsiana al del vanadio-circón, el verde supera ligeramente a la eskolaita Cr2O3, que se ha tomado como referencia, y en el caso de la perovskita negra sus valores SRI muy bajos (SRI = 0 en el caso del polvo) y asociados a altos valores de emisividad en el infrarrojo medio la hacen interesante como pigmento para sustratos absorbentes en colectores solares. La capacidad fotocatalítica sobre Naranja II indica valores de periodo de semivida en torno a 55-70 min, inferiores a los medidos en los circones de referencia (110-190 min).Optimized compositions of a four-color CMYK plus a green pigment have been prepared by the ceramic method: cobalt doping in Celsian (Ba0,9Co0,1)Al2Si2O8 (cyan), chromium in armalcolite (MgFe)(Cr0,2Ti2,8Fe)O10 (magenta), nickel in geikielite (Mg0,5Ni0,5)TiO3 (yellow), the perovskite CrNdO3 (green) and the same perovskite mineralized with alkaline earth fluorides (BaF2 and MgF2) (black). Both pigment powder and glazed sample in a conventional double firing frit (1050 °C) have been characterized with respect to its colorimetric performance by the model CIEL*a*b*, its cooling capacity (as cool pigments) by the measurement of the solar reflection index SRI and its photocatalytic capacity by means of the Orange II degradation test. The obtained results are compared with those obtained with commercial pigments of the CMY family of the zircon. The results indicate that the coloration of the powders and the enamelled samples is more intense, with L* values lower than the zircon homologous pigments, whereas the obtained chroma with the pigments of the zircon is better (b* negative for cyan, a* positive for magenta and b* positive for yellow). Regarding its cooling capacity, the results indicate high SRI values for all samples. In the case of Celsian SRI is higher than for vanadium-zircon, the green of perovskite slightly exceeds the eskolaite Cr2O3 value that is taken as reference. In the case of the black perovskite, very low SRI values are measured (SRI = 0 in the case of powder) and associated with high middle-infrared emissivity values, making it interesting as a pigment for absorbent substrates in solar collectors. The photocatalytic capacity over Orange II indicates half-life values around 55-70 minutes, lower than those measured in zircons (110-190 minutes).Los autores agradecen la financiación de la Universidad Jaume I (Proyecto P1.1B2015-19) y del Ministerio de Educación (Proyecto MAT2015-69443-P)

Recycling of Cr/Ni/Cu plating wastes as black ceramic pigments

The non-ferrous metal industry, such as Cr/Ni/Cu plating, produces acid sludge which is usually neutralized with lime slurry in batch processes, and the resulting waste is dewatered by vacuum filtration or filter-pressing. Dewatered sludge contains calcium sulphate (CaSO4) coming from the neutralization process, as well as transition metals (Cr, Ni and Cu), oil, grease and suspended solids. In this communication, two residual sludges from Cr/Ni/Cu plating have been dried (110 C) and fired (1100 C), and both dried (gray coloured) and fired powders (black coloured) have been characterized by DTA-TG, XRD and SEMEDX techniques. XRD shows only quartz crystallization in dried samples, while NiCr2O4 chromite spinel and NiO periclase crystallize in fired powders, along with CaSO4 anhydrite and CaSiO3 wollastonite. The powders have been introduced as ceramic pigments into three different conventional glazes: a) a lead bisilicate (PbO.2SiO2) double fire frit (1000 C), b) a double fire frit with low lead content (1000 C), and c) a double fire frit without lead (1050 C). Glazed samples were characterized by UV-Vis-NIR (diffuse reflectance) and CIEL⁄a⁄b⁄ (color parameters). Dried powders induce glaze defects (pin-holing and crawling), but fired powders did not show these faults exhibiting more intense (higher L⁄ ) and yellowish (higher b⁄ ) black colors than the standard spinel

New chromium doped powellite (Cr–CaMoO4) yellow ceramic pigment

A new chromium doped powellite (Cr–CaMoO4) yellow ceramic pigment alternative to yellow of praseodymium-zircon has been synthesised and characterised in order to analyse: (a) the stoichiometry of the solid solution, (b) the effect of the dopant concentration under the pigmenting properties, (c) the effect of the chromium precursor and mineralizers addition, (d) the effect of the synthesis method. The composition CrxCaMo1−xO4x=0.075 using K2Cr2O7 or Cr2O3 as chromium precursors fired at 1000–1100 °C produces a yellow colour, slightly lower in intensity than the commercial praseodymium-zircon yellow pigment in double (1000 °C) or single firing (monoporosa—1080 °C or porcelainized stoneware—1200 °C) ceramic glazes. By a coprecipitation method with ammonia, and firing at 950 °C, the yellow ceramic pigment glazed in a conventional CaO–ZnO–SiO2 glaze (monoporosa glaze, 1080 °C) shows a yellow colour similar to the commercial praseodymium-zircon yellow pigment. However the release and possible mobilization of the Cr (VI) should be controlled in order to get its industrial implementation.Authors acknowledge the financial support given by MEC (MAT2012-36988-C02-01 project)

Karrooite green pigments doped with Co and Zn: Synthesis, color properties and stability in ceramic glazes

The solid-state synthesis and stabilization of Co doped (Mg1−xCoxTi2O5), Zn doped (Mg1−xZnxTi2O5) and Co- and Zn-codoped karrooite solid solutions (Mg0.8−xZn0.2CoxTi2O5 and (Mg0.5Zn0.5)1−xCoxTi2O5) were investigated. In addition, the optical spectra, color properties and technological performance of (Co,Zn)-karrooite compositions as new green ceramic pigments were also analyzed. XRD characterization revealed for the first time the high solid solubility of Zn2+ in MgTi2O5 karrooite at 1200 ºC (between 60 and 80 mol% per Mg or karrooite formula unit). In contrast, the reactivity and stabilization of karrooite phase decreased in the case of Co2+ doping. Interestingly, codoping with Zn2+ ions at high molar ratios (Zn:Mg ratio equal to 1:1) enhanced the reactivity and enabled the stabilization of (Co,Zn)-MgTi2O5 karrooite solid solutions, even with high Co2+ loadings (20 mol% per karrooite formula unit). The (Co,Zn)-MgTi2O5 pigments exhibited yellowish-green colors associated to Co2+ ions allocated in octahedral M1 and M2 sites of karrooite lattice, and becoming more intense and less yellow the higher the Co content. However, Zn2+ codoping produced less saturated green colors with similar green but lower yellowish hues. The obtained pigments were not stable enough within the tested ceramic glazes, giving rise to turquoise colorations due to cobalt leaching and incorporation into tetrahedral sites of the glassy phase. The stability of Co-karrooite green pigments was higher in a Ca- and Zn-enriched ceramic glaze (B) fired at a higher temperature (1050 °C)

Photocatalytic Glazed Tiles

A parent glass in the SiO2–CaO–ZnO–B2O3–K2O–Al2O3 system, deposited and processed by the monoporosa firing method (1085 °C), was coated using a sol–gel procedure and by serigraphy with silica, bismuth oxide, zirconia, and anatase with thermal treatment at 600 °C. The photocata- lytic activity of the samples determined by degradation in the Orange II dye test shows that a first-order reaction according to the Langmuir- Hinshelwood model is followed. From the UV-Vis-NIR results the band gap calculated is around 3.5 eV for the parent glass and that with a silica coating, and slightly lower for the other coatings. The needle-shaped microstructure of the parent glass shows the best photocatalytic results in agreement with the literature. The preserved zircon microstructure can explain the relatively high results for the silica coating, which unexpect- edly showed better results than both the anatase and tetragonal zirconia coatings. Finally, the interaction with the parent glass can explain the relatively high results of the bismuth oxide sampl

New chromium-calcium titanate red ceramic pigment

Synthesis and characterization of a new chromium- calcium titanate red ceramic pigment is described in this communication. The pigment is based on the solid solution of chromium (IV) in calcium titanate and was characterized as red-brown pigment in a CaO- ZnO-SiO2 transparent glaze used for ceramic tiles (1080oC). XRD, UV-Vis-NIR spectroscopy and CIE-L*a*b* techniques of characterization have been employed. The L*a*b* valour of the optimal pigment with 0,015 mol/mol of chromium fired at 1100oC with a soaking time of 3 hours and 5% weight added to the transparent glaze is 59.3/12.5/9.5. Likewise 5%w. addition of NHCl used as flux agent increase b* and decrease L* valour (L*a*b*=45.2/15.3/5.3)

Iron and chromium doped perovskite (CaMO3 M = Ti, Zr) ceramic pigments, effect of mineralizer

Solid solutions Ca(DxM1−x)O3 (M = Ti, Zr and D = Fe,Cr), have been studied as ceramic pigment in conventional ceramic glazes using 0.5 mol/mol of NH4Cl as flux agent by solid state reaction and by ammonia coprecipitation route. Ca(CrxTi1−x)O3 compositions obtained without addition of NH4Cl as mineralizer, produce pink color in glazes at low x but CaCrO4 crystallizes when x increases, producing undesired green colors. The crystallization of chromates can be avoided using NH4Cl as mineralizer, giving a complete solid solution that produce pink color in glazes at low x and dark blue shades at high x. Coprecipitated sample produce blue colors at low x and at low temperature than ceramic sample (1000 °C instead 1200 °C for CE sample). Cr4+ ion acts as red chromophore, but at higher x values (blue samples) Cr3+ ion entrance affects the color. Ca(FexTi1−x)O3 system crystallizes perovskite CaTiO3 and pseudobrookite Fe2TiO5 together with rutile as residual crystalline phase, glazed samples change from a yellow to a pink color associated to the increase of pseudobrookite with firing temperature. Ca(FexTi1−x)O3 and Ca(CrxZr1−x)O3 systems crystallize perovskite CaZrO3 and zirconia (ZrO2) in both monoclinic and cubic polymorphs, but iron or chromium oxides are not detected in the powders. Coprecipitated sample stabilises cubic form. The solid solution is not reached completely in these samples and is not stable in glaze