Phase transformation of FeCr2O4 to (Fe,Cr)2O3 solid solution pigment powders: Effect of post-heating temperature

Iron chromite powders were synthesized via solution combustion route using iron(III) nitrate nonahydrate and chromium(III) nitrate nonahydrate as starting materials, as well as glycine–urea, glycine–citric acid, and glycine–ethylene glycol mixtures as fuels. The effect of postheating at different temperatures on the structure, molecular, microstructure, and chromatic properties of powders and tiles colored by in-glaze powders was studied. The X-ray diffraction patterns showed that as-synthesized powders were obtained in crystalline FeCr₂O₄ phases moreover, postheating of the powders led to d-space shift and oxidation and formation of (Fe,Cr)₂O₃ solid solution phase regardless of fuel type. Phase transformation of FeCr₂O₄ to (Fe,Cr)₂O₃ solid solution was observed at 500/750°C depending on the dominant phase of as-synthesized particles. Fourier transform infrared analysis illustrated that the band positions of octahedral M–O and tetrahedral M–O bonds were shifted due to Fe cations movement from their position and lattice shrinkage by increasing of post-heating temperature. Moreover, scanning electron micrographs showed that Fe_0.7Cr_1.3O₃ semispherical fine particles were formed from porous spongy FeCr₂O₄ particles due to oxidation and phase transformation during the postheating. Furthermore, chromatic properties of the samples were represented. The color properties of the pigments showed that the formation of brown pigments is provided with the phase transformation from FeCr₂O₄ to (Fe,Cr)₂O₃ at a temperature of up to 750°C. Moreover, increasing the color purity to this temperature is related to the removal of residual carbonaceous matters. The chromatic properties of the glazed tiles colored using the pigments showed that postheating between 250 and 500°C led to more brown appearance.     

Production and characterisation of iron-chromium pigments and their interactions with transparent glazes

In this study, production and characterisation of pigments by using less expensive raw materials such as limonite and chromite was undertaken. The resulting pigments were characterised by using X-ray diffraction (XRD) and UV-Vis spectrophotometer. The colour of glazed tiles containing 3 wt.% pigment change from dark brown to light brown depending on the calcination temperature and limonite content. With pigments prepared with 50% limonite content calcined at 1250 °C, the chocolate brown colour was obtained corresponding to the commercial brown pigments. An iron-chromium black pigment was synthesised from a mixture of pure chromium (III) oxide (Cr₂O₃) and iron (III) oxide (Fe₂O₃) powders and was used to determine possible interactions between a pigment and a transparent glaze. The interactions were studied using a scanning electron microscope (SEM) attached with an energy dispersive X-ray spectrometer (EDX). The results showed that black pigment particles give brown colour to the glaze. EDX analysis on pigment crystals embedded in the glaze clearly showed that Zn and Mg diffused into pigment crystals and caused a change of colour from black to brown.     

Synthesis of (Fe,Cr)2O3 solid solution pigment powders for ink application

Iron chromite pigment was synthesized via solution combustion using iron(III) nitrate nonahydrate and chromium(III) nitrate nonahydrate as starting materials, and glycine, urea, citric acid, and ethylene glycol as fuels. The effect of postheating temperature on the structure, microstructure, and chromatic properties of the synthesized powders was also studied. X-ray diffraction patterns showed that the as-synthesized powders were amorphous to crystalline FeCr₂O₄ phases, depending on fuel type. Moreover, regardless of the fuel type, postheating led to the d-space shift and oxidation and formation of (Fe,Cr)₂O₃ solid solution. Phase transformation of FeCr₂O₄ to (Fe,Cr)₂O₃ solid solution was observed at 500/750°C depending on the dominant phase present in the as-synthesized particles. Fourier transform infrared analysis illustrated a shift in the band position of octahedral M–O and tetrahedral M–O bonds due to the movement of Fe cations and the lattice shrinkage by increasing the postheating temperature. Moreover, scanning electron micrographs showed that Fe_0.7Cr_1.3O₃ semispherical fine particles consisted mainly of porous and spongy FeCr₂O₄ particles due to the oxidation and phase transformation during postheating. According to chromatic measurements, the ink prepared by using the powders synthesized in the presence of glycine and post-heated at 500°C showed reddish-brown color which could be considered a promising candidate for tile decoration application. Furthermore, rheology studies revealed that the prepared ink showed non-Newtonian shear thinning behavior.     

The influence of Ca2+ and Zn2+ doping on the development of sustainable pigments based on GdFeO3 perovskite: From a reddish colour towards a pure black

Black pigments are very commonly used and arouse widespread interest in the ceramic industry. Nevertheless, these pigments contain toxic elements that are detrimental to human health. In view of this, the present work is focused on the development of sustainable black pigments prepared by a coprecipitation method at 1200 °C. Samples with the nominal formula (Gd_1–xCa_x)(Fe_0.95Zn_0.05)O_2.975–x/2 (x = 0.00, 0.05, 0.10) showed single-phase orthorhombic perovskite. The presence of dopants played an important role in the reduction of Fe³⁺ to Fe²⁺ and caused different local distortions in the structure which explained the final black colouration of these pigments in comparison with the red GdFeO₃ sample. The loss of symmetry and the increase in the number of d-d transitions of iron may explain the aforementioned changes. Co-doped pigments reached low C* values, improving on the purest black colour obtained in a commercial black ceramic pigment, which contains toxic elements. In addition to presenting good NIR solar reflectance values of up to 8%, the final colours of these pigments were also stable after their application in a commercial transparent glaze at 1080 °C that could be used for tiles.     

Sol–gel and sonochemically derived transition metal (Co,Ni, Cu,and Zn) chromites as pigments: A comparative study

Cobalt chromite based pigments Co_1−xM_xCr₂O₄ (M=Ni, Cu, and Zn) with different transition metal concentrations (0≤x≤1 with a step of 0.25) have been synthesized applying two aqueous synthesis approaches: sol–gel and sonochemical synthesis routes. The heat treatment of precursor powders was performed between 600 and 800 °C. XRD analysis of the obtained powders revealed that all samples fabricated by sol–gel method have crystallised in a spinel structure, whereas sonochemical synthesis of Ni chromite at lower calcination temperatures showed the formation of mixtures of oxides. In addition, the degree of crystallinity and shaping of sonochemically obtained compounds is lower than sol–gel derived products. The chromites with a higher nickel concentration displayed green colour, while Cu-substituted pigments were nearly black. The spinels with a higher Zn amount were yellowish green.     

Synthesis of Y(Al,Cr)O3 red pigments by co-precipitation method and their interactions with glazes

New red pigment based on the system YAl_1−yCr_yO₃ (y = 0.01–0.1) was synthesized by co-precipitation method. The precipitant was attained by mixing solutions of yttrium, aluminum and chromium nitrates, respectively, and addition of ammonia as the precipitator. The effects of chromium as dopant and glaze composition on the color shade of resulting pigments were studied. EDX analysis of the prepared pigment particles, which was embedded in glaze, showed the occurrence of reactions between some glaze constituents and pigment particles. Accordingly, a glaze which was enriched in Al₂O₃ and poor in ZnO was more suitable in point of achieving a reddish shade. The resulting pigments were characterized by using X-ray diffraction (XRD), SEM and UV–vis spectrophotometer.     

Environmental-friendly yellow pigment based on Tb and M (M = Ca or Ba) co-doped Y2O3

A yellow inorganic ceramic pigment with general formula Y_1.86?xM_xTb_0.14O_3?x/2 (M = Ca and/or Zn) with x = 0.06, 0.32 and 0.64 were synthesized by a modified Pechini method. XRD, SEM and HRTEM/EDX analysis showed the formation of solid solution at 1300 °C when x = 0.06 and 0.32. The best b* yellow coordinates were obtained for Ca and Zn co-doped Y_1.86Tb_0.14O₃ samples. The intensity of the yellow colour in the samples is related to the presence of Tb⁴⁺ ions. Samples with higher concentration of Tb⁴⁺ ions lead to a better yellow colour. The chemical stability of these pigments was determinate in an industrial glaze. The glazing tests indicated that the powder samples with x = 0.06 and 0.32 fired at 1300 °C were stable in the glaze. These results make it a potential candidate for environmental friendly yellow ceramic pigment to be used in applications such as pigment for glazes or inkjet printers.     

Solid solutions of mixed metal Mn3−xMgxFe4(PO4)6 orthophosphates: Colouring performance within a double-firing ceramic glaze

Solid solutions of mixed metal Mn_3−xMg_xFe₄(PO₄)₆ orthophosphates (x = 0, 0.5, 1, 1.5, 2, 2.5, and 3) were prepared for the first time (from coprecipitate powders calcined up to 1000 °C) and characterized by thermal analysis, XRD, SEM/EDX, UV-vis-NIR spectroscopy and colour measurements (CIE-L*a*b*). Orthophosphate (Mn,Mg)_3−yFe_4+z(PO₄)₆ solid solutions isotypic to Fe₇(PO₄)₆ structure (triclinic P-1(2) spatial group) formed successfully as the major crystalline phase within the studied range of compositions, accompanied only by variable quantities of α- and/or β-Mg₂P₂O₇ diphosphates as secondary phases. Noteworthy, the obtained solid solutions were tested as potential ceramic dyes and exhibited an interesting interaction upon enamelling within a double-firing ceramic glaze: considerable amounts of Fe segregated from the solid solutions to be stabilized as hematite particles (α-Fe₂O₃) in the ceramic glaze and conferring the glaze an intense dark-brown colouration, which was almost independent of the amount of Mg doping. Thus, the obtained solid solutions with a minimized Mn content (especially Mg₃Fe₄(PO₄)₆ composition, without Mn) could serve as low-toxicity Fe reservoirs to stabilize hematite in double-firing glazes and produce an interesting dark-brown colouration, being an alternative to other brown ceramic pigments containing hazardous metals (i.e. Cr, Ni, Zn, or Sb).     

Solution combustion synthesis of FeCr2O4 powders for pigment applications: Effect of fuel type

Solution combustion synthesis of iron chromite was reported using iron(III) nitrate nonahydrate and chromium(III) nitrate nonahydrate as starting materials, as well as glycine, urea, citric acid, and ethylene glycol as fuels. The influence of fuel type on the structure, molecular, microstructure as well as chromatic properties of samples was investigated. The X-ray diffraction (XRD) patterns showed that unlike themodynamical prediction, glycine fuel led to strongest combustion and consequent highest XRD peak intensities and lower lattice parameters. Moreover, the change of fuel type and mixing of fuels affected XRD data. Fourier transform infrared analysis showed that the band position of Cr–O and Fe–O bonds were shifted to higher frequencies by using of fuels with weaker combustion reactions. In addition, scanning electron micrographs showed that different morphologies of FeCr₂O₄ particles were obtained depending on the fuel type and ratios. Energy-dispersive X-ray spectroscopy analysis of the samples showed that oxygen concentration of samples was less than that of stoichiometric ratio of FeCr₂O₄ due to local reducing atmosphere. Furthermore, chromatic properties of the powders showed that the pigment synthesized with glycine fuel has a better and lighter grayish brown color than the other ones and can be used as a suitable industrial candidate to create a brown color in the ceramic glaze.     

Relationship between certain ceramic roofing tile characteristics and biodeterioration

This paper examines the relationship of certain red ceramic roofing tile properties to roofing tile biodeterioration. The following properties were studied: apparent porosity, roughness, and the presence or absence of two types of coatings.The effect of apparent porosity was studied by varying the peak firing temperature of a standard industrial red ceramic roofing tile composition and by preparing several clay mixtures, of different chemical and mineralogical composition, that were fired at various peak temperatures. The effect of roofing tile roughness was determined by either polishing or sanding fired standard red roofing tiles. A waterproof ceramic glaze coating and a photocatalytic coating were formulated to analyse the effect of the presence of different types of coatings. Roofing tile bioreceptivity was evaluated with a method developed in a previous study using the cyanobacteria Oscillatoria sp, which enabled roofing tile resistance to microbial colonization to be determined.As expected, bioreceptivity rose as apparent porosity (measured as water absorption) increased, enabling possible water retention, which favours biological growth. Similarly, greater roughness encouraged micro-organism adhesion and raised bioreceptivity. It was found that, after prolonged exposure periods (several months) under very favourable conditions for biological colonization, roofing tiles coated with the waterproof ceramic glaze were colonized. However, glazed standard red roofing tiles covered with a TiO₂ photocatalytic coating exhibited practically no biological growth under the test conditions used, even after long exposure times, owing to the chemical-physical effect of the TiO₂-based coating.     

New pink ceramic pigment based on chromium (IV)-doped lutetium gallium garnet

Lutetium gallium garnet codoped with chromium and calcium (Ca,Cr:LGG) and lutetium gallium garnet with chromium as single dopant (Cr:LGG) have been studied. Samples with Ca_xCr_xLu_3−2xGa₅O₁₂ (x = 0, 0.05, 0.10, 0.15, 0.2, 0.4, 0.6,) and Cr_xLu_3−xGa₅O₁₂ (x = 0.15 and 0.6) compositions were prepared by solid state reaction and the fired samples (1250 °C/6 h) were characterised by XRD, lattice parameters determination, UV–vis–NIR spectroscopy, CIEL*a*b* measurements and SEM/EDX. Moreover, the samples with calcium were tested as ceramic pigments in a conventional glaze matrix. In the Ca,Cr:LGG system solid solutions incorporating both Cr(III) and Cr(IV) ions were obtained. Cr(IV) occupies basically dodecahedral sites substituting for Lu (III) and is the predominant oxidation state up to x = 0.20 composition, giving a pink colouration in the ceramic glaze matrix. In the Cr:LGG system, only Cr(III) enters in solid solution occupying octahedral positions and producing green shades.     

Effects of starch addition on the characteristics of CoAl2O4 nano pigments

Nanocrystalline cobalt aluminate spinel, CoAl₂O₄, was prepared via a microwave‐assisted solution combustion process applying various mixtures of urea, glycine, and starch as a novel mixed fuel. The effects of starch addition (0, 10, 20, and 30 wt%) on the physical characteristics (e.g. crystallite size and colour) of the blue nano pigments were also investigated. The resultant powders were characterised by means of X‐ray diffraction, scanning electron microscopy, electron dispersive X‐ray analysis, and CIE L*a*b* colour measurements. The presence of a CoAl₂O₄ spinel lattice after calcination of precursors at 600 °C was confirmed by X‐ray diffraction patterns, and the crystallite sizes were ca. 10–39 nm. Colorimetric data pointed to the formation of bright‐blue pigments at low levels of starch addition. Scanning electron microscope images showed that starch enrichment reduced the agglomeration and size of synthesised nanoparticles.     

Nanocomposite Fe2O3–SiO2 inclusion pigments from post-functionalized mesoporous silicas

High-surface mesoporous silicas with different pore sizes were employed for the first time as silicon precursors in the synthesis of reddish Fe₂O₃–SiO₂ inclusion pigments. Interestingly, the size of included Fe₂O₃ nanoparticles was partially controlled through confinement effects into silica mesopores. Notably, impregnated samples showed a more homogeneous and efficient encapsulation of smaller and monodisperse hematite nanoparticles (sizes around 10–35 nm). Moreover, they resulted in an improved reddish color at 1000 °C within a ceramic glaze. The best red shade (a* ≈ 18) was associated to nanocomposite with smaller hematite nanoparticles (around 5 nm). These promising results suggest the possibility to improve the reddish coloration and thermostability of Fe₂O₃–SiO₂ ceramic pigments through and adequate control of confinement effects into sintered mesoporous silicas.     

Color matching algorithms in ceramic tile production

In the present work, the possibility of transferring in the ceramic tiles production the know-how developed in the field of the paints by using the Kubelka–Munk theory, in the form used for opaque surface coatings, have been evaluated. Five different target colors have been chosen as target and tried to reproduce with an industrial glaze in a cycle for fine porcelain stoneware tiles. Four industrial pigments have been chosen as basic stains for the formulations. The results show a good efficiency of the color matching algorithm applied to pigments for glazes for fine porcelain stoneware tiles. All the formulations, in fact, have allowed to obtain a value of ΔE^* lower to the accepted limit.     

Improvement of promoters on the Fischer–Tropsch activity of mechanically mixed Fe catalysts

The precipitated Fe₂O₃ was promoted with K, Cu, Zn and Al by impregnation and mechanical mixing. Their activity for Fischer–Tropsch (FT) synthesis was tested in fixed bed reactor under the conditions of 503 K and 1.6 MPa syngas (H₂/CO = 2). The Fe catalysts co-promoted by K, Cu, Zn and Al showed increasing CO conversion with time on stream. At present, the improvement is ascribed to the increased resistance to water oxidation on active sites and the further formation of active sites during FT synthesis with the addition of K, Cu, Zn and Al to Fe catalysts. The carbon deposition is not responsible for the variety of catalytic activity in this study.     

Low Temperature Sintering and Enhanced Piezoelectricity of Lead‐Free (Na0.52K0.4425Li0.0375)(Nb0.86Ta0.06Sb0.08)O3 Ceramics Prepared from Nano‐Powders

(Na_0.52K_0.4425Li_0.0375)(Nb_0.86Ta_0.06Sb_0.08)O₃ powders were synthesized via sol–gel and solid‐state reaction methods as a raw material for the preparation of the ceramics. Dependence of piezoelectric properties and microstructure on sintering temperatures was investigated in this study. Sol–gel‐derived nano‐powders could be densified at a lower temperature of 940°C and exhibited excellent electrical properties after sintering at 1020°C (d₃₃ = 424 pC/N, d₃₃^* = 780 pm/V, k_p = 52.1%, and T_c = 265°C). The enhanced electric properties were most likely due to the coexistence of orthorhombic and tetragonal phase in the samples at room temperature, homogenous microstructure with fine grain and high density.     

Improved coloristic properties and high NIR reflectance of environment-friendly yellow pigments based on bismuth vanadate

Herein, fine powders of yellow pigments based on BiVO₄ were successfully prepared in two crystalline forms, tetragonal zircon-structured and monoclinic scheelite-structured, through a ethylene glycol-assisted method subjected to a thermal treatment at two different temperatures. The obtained materials were brightly colored with different hues of yellow, exhibited high reflection in the near-infrared region and showed visible luminescence under excitation by UV light. The new preparation method had a considerable effect on chromatic properties of the prepared scheelite-structured BiVO₄ pigments. The sample with the most vivid and bright shade of yellow was found to have the L^*a^*b^* and L^*C^*_ab h^*_ab color coordinates of (87.28, 0.37, 91.53) and (87.28, 91.53, 89.79), which are indicative of exceptionally good chromatic properties superior and/or comparable to those of other inorganic yellow pigments, both commercially available and recently described. In addition, the NIR reflectance of this powder was very high (≥?80%).     

Zircon-free frits suitable for single fast-firing opaque wall tile glazes and their industrial productions

Wall tile glazes with a smooth surface texture, high glossiness, and whiteness are usually based on zirconium containing frits. However, these frits are quite expensive and therefore, there have recently been certain attempts to lower the production cost such as taking suitable glass–ceramic glaze systems into an account. With the present work, the frit-based glaze compositions belonging to the K₂O–MgO–CaO–ZnO–Al₂O₃–B₂O₃–SiO₂ glass–ceramic system were studied to prepare newly synthesized wall tile glazes for industrial single fast-firing. The design of a glass–ceramic glaze for this type of tiles should ensure that the selected frit precursor is technically and commercially compatible with the manufacturing conditions generally used in the production of glazed ceramic wall tiles. The aim of the study is to develop zircon-free, frit-based, glossy opaque glass–ceramic glazes for wall tiles by optimizing the CaO/MgO and adjusting the Al₂O₃/alkali ratios in the starting frit compositions. Frit production, glaze preparation, application, and single fast-firing of wall tiles were, first of all, conducted under laboratory working conditions and then, successful recipes were adapted to the relevant industry. The frit crystallization capability and crystallization temperature range were determined by differential thermal analysis (DTA). Thermal expansion coefficient values of glazes were determined by a dilatometer. Characterization of single fast-fired glass–ceramic glazes was made by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) techniques. Colour and gloss analyses of the final glazes were measured with a spectrophotometer and a gloss meter, respectively.     

Characterization of blue CoAl2O4 nano-pigment synthesized by ultrasonic hydrothermal method

Nano-sized CoAl₂O₄ pigments, which have received significant attention as a coloring agent in glaze and bulk tile compositions, were successfully synthesized by substituting mechanical stirring during hydrothermal process with ultrasonic irradiation. Difference in physicochemical and optical properties of the CoAl₂O₄ pigments prepared by an ultrasonic-assisted-hydrothermal method was characterized using simultaneous thermo-gravimetric and differential thermal analysis (TG–DTA), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), diffuse reflectance spectroscopy, CIELAB colorimetric analysis, and testing in ceramic glazes and bodies. The ultrasonic-assisted CoAl₂O₄ pigments present a narrow particle size distribution with vivid blue color, and better thermal stability, allowing their use for ceramic inks processed at high temperature. Application of ultrasonic irradiation during the hydrothermal process produces nano-sized powders with better physicochemical and optical properties.     

New red pigments based on Li3AlMnO5 for NIR reflective cool coatings

The exploration of new red pigments based on transition elements is of great practical value in the field of inorganic pigments, since the red coloured pigments have unique applications in paints, ceramic tiles, cosmetics, etc. Here we mainly reported a new class of eco-friendly red pigments based on substituted Li₃AlMnO₅ (LAMO) and briefly state about the other rock salt layered structure Li₃GaMnO₅ (LGMO). The solid-state synthesized powders were crystallized to monoclinic structure having Mn^IV(1)_2b and Mn^IV(2)_4g site. The absorption bands in the synthesized samples mainly arises due to the octahedrally coordinated Mn^IVO₆ in the 4g site. Among the synthesized samples, LAMO: 0.10Ti⁴⁺ showed exemplary chromatic properties. The doping of tetravalent Ti⁴⁺ ions in the Mn⁴⁺ sites altered the Mn^IV(2)O₆ bond lengths and increased the crystal field around the absorption band attributed to the ⁴A_2g→⁴T_2g transitions. The ball milled LAMO: 0.10Ti⁴⁺shows the a* value of 40.05, which is higher than that of the commercially available red iron oxide pigments (a* = 28.9). Meanwhile, the brighter red powder LAMO: 0.10Ti⁴⁺ demonstrated appreciable thermal and chemical stability. From the thermal evaluating study, we observed that, LAMO: 0.10Ti⁴⁺ pigment coated roof panels showed a temperature difference of (3.2 °C) compared to the bare roof panel (3.7 °C). We estimated the coating's performance of the LAMO: 0.10Ti⁴⁺ in concrete block, metal plate and ceramic tile. In these substrates, the pigment possesses distinctly elevated NIR‐reflectance, which makes these materials worthwhile for cool coating applications.