Use of industrial wastes in the formulation of olivine green pigments

This work describes the formulation and synthesis of Ni-olivine green pigments from industrial wastes, namely foundry sand and a sludge resulting from the wastewater treatment of the Ni/Cr galvanising process. This second one is considered as hazardous waste since the leached levels of nickel and chromium are above legal concentrations. Pigments were prepared by the solid state reaction method and Ni₂SiO₄ is formed at only 1050 °C. SiO₂ (in excess) and NiCr₂O₄ are present as secondary phases. By using pure reagents and following similar processing conditions, the Ni-olivine phase is only observed at 1200 °C. The green colour of the pigments is due to spin-allowed transitions of Ni²⁺ in octahedral M1 and M2 positions. The sample prepared from wastes shows a stronger and darker green hue. The colouring performance of ceramic glazes and bodies is also optimal, confirming the potential of the use of such wastes for ceramic pigments production.     

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.     

Formulation and characterization of black ceramic ink for a digital ink-jet printing

Formulation of black ceramic ink and its ink-jet printability on a glass substrate were investigated. The thermal and chemical stabilities of CoFe_2-xCr_xO₄ and Ni_0.925Mn_0.075Fe_1.875-xCr_xMn_0.125O₄ black inorganic pigments were analyzed with various amounts of Cr substitutions. The ceramic ink was prepared using the pigment composition that demonstrated color stability during the high temperature glazing process with a minimal Cr substitutional amount. After the dispersion stability and rheological property were optimized, the ceramic ink was suitably jetted from a print head as a single sphere-shaped droplet without satellite droplets. To improve the printability of the ceramic ink, the glass substrate was treated with a perfluorooctyl trichlorosilane (PFTS) solution. As a result, the PFTS surface treatment increased the contact angle of the ceramic ink droplets on the glass substrate and effectively minimized the ink spreading phenomena.     

Synthesis of black pigments containing chromium from leather sludge

The black ceramic pigments with spinel structure have been prepared by using Cr-rich leather sludge in this paper. The washed Cr-rich leather sludge calcined at 1100 °C for 1 h as chromium oxide precursor (named as CA) was mixed with an appropriate proportion of other industrial metallic oxides, followed synthesizing black ceramic pigment by sintering. Both non-washed and washed sludge fired at 1100 °C were characterized by X-ray fluorescence (XRF) in order to determine their chemical compositions and X-ray diffraction (XRD) analysis to confirm that CA mainly contains Cr₂O₃ crystal phase. The results show that CA could be used as a source of chromium to prepare black pigment. The crystalline phases of obtained pigments were characterized by XRD. Furthermore, the morphology as well as the composition of pigments was investigated by scanning electron microscopy (SEM) and energy dispersion spectroscopy (EDS). The color coordinates of pigments were examined and compared with the commercial pigments based on CIE-L* a* b* values measured using UV–vis spectroscopy. The obtained pigments sintered at 1200 °C with 35–55 wt% content of CA possess the excellent black spinel structure and color effect. Under optimized conditions, the pigment has low average spectral reflectance (7%).     

Colour in ceramic glazes: Efficiency of the Kubelka–Munk model in glazes with a black pigment and opacifier

In this study the efficiency of the Kubelka–Munk model (already known and consolidated in other industrial sectors) was evaluated in the prediction of the colour of an opaque ceramic glaze obtained by a mixture of black pigment (spinel Ni–Fe–Cr) and zircon opacifier (ZrSiO₄). Glazes with different percentages of black pigment and opacifier were prepared to determine the absorption and scattering optical constants from the reflectance curves measured with a spectrophotometer. After the physical and chemical characterization of the glaze components (frit, pigment and opacifier), suggestions for the adaptation of the Kubelka–Munk model were made to facilitate the experimental procedure of analysis. The result obtained with the adapted Kubelka–Munk model was in good agreement with the experimental reflectance curves. The reproduction of the desired colour was possible with a reduced number of experiments and the model made it possible to correlate the colour with the added pigments concentration facilitating the formulation step.     

Ceramic pigments obtained by sol-gel techniques and by mechanochemical insertion of color centers in Al2O3 host matrix

Nanocrystalline pigments for ceramic glazes have been obtained by mechanochemical insertion of Fe and Ti in an α-Al₂O₃ host matrix (Fe and Ti oxides were reduced by high energy milling with metallic Al with subsequent formation of additional Al₂O₃ by oxidation of Al(0)). The powders have been characterized by X-ray diffraction, laser granulometry and by surface area and porosity measurements. Sol-gel techniques have also been used in order to obtain pigments with pure Al₂O₃ and Cr or Fe/Ti-doped Al₂O₃. Pigments have been prepared using Al(III)-alkoxides or Al(III)-inorganic salts, obtaining products with different characteristics in the two cases. Pigments have been studied by X-ray diffraction, surface area and porosity measurements and by the analysis of electrochemical reactivity in aqueous suspensions. Coloring properties of pigments obtained by mechanomaking and by sol-gel techniques have been tested in ceramic glazes; their properties have also been analyzed by insertion in ceramic bodies for glazed gres (porcelain) technology.     

Synthesis,through pyrolysis of aerosols,of YIn1−xMnxO3 blue pigments and their efficiency for colouring glazes

Mn-doped YInO₃ blue pigments have been synthesised at a much lower temperature (1100 °C) than that required by the traditional solid state method (1400 °C). The developed procedure, which is based on the pyrolysis at 600 °C of aerosols generated from aqueous solutions of Y, In and Mn nitrates followed by an annealing treatment at 1100 °C, yields spherical pigments particles with heterogeneous size in the optimum range required for ceramic applications (<10 μm). The amount of Mn introduced in the YInO₃ matrix has been systematically varied in order to evaluate the effects of the Mn content on the colour properties of the pigments. It has been found that the optimum pigment composition (bluer colour with the lowest Mn content) is given by the formula YIn_0.90Mn_0.10O₃. The technological performance of these YIn_1−xMn_xO₃ blue pigments has also been evaluated by testing their efficiency for colouring ceramic glazes of different composition (boracic and plumbic) and properties, aiming to find a less toxic alternative for the Co-based pigments commonly used by the ceramic industry.     

Effect of the milling process on the properties of CoFe2O4 pigment

In this study, CoFe₂O₄ pigments were synthesised using both co-precipitation and conventional ceramic methods. Pigment particles prepared using the conventional ceramic method were subsequently milled to submicron size. The effects of the solvent, dispersant and milling type in the milling process were investigated. This study showed that planetary milling in a diethylene glycol (DEG) medium with sodium tripolyphosphate (STPP) was an effective method for producing submicron-sized pigment powders from pigments synthesised using the conventional method. With this method, submicron-sized pigment particles (approximately 190 nm) were obtained after milling for 4 h. Planetary milling was more efficient in reducing particle size compared to attrition milling. Co-precipitated pigment had a more intense black colour, due to the nanoscale particle size (<100 nm). However, conventional ceramic pigments also had an adequately intense black colour that increased after milling compared to unmilled conventional pigments. When considering production of industrial scale submicron-sized pigments, the milling of these pigments to submicron size can be a good alternative method for the production of ink colourants.     

Praseodymium-doped cubic Ca–ZrO2 ceramic stain

The cubic Ca–ZrO₂ structure has been used as host for preparing a yellow ceramic stain using praseodymium as dopant. Samples with Ca_xPr_0.1Zr_0.9−xO₂ (X=0.14, 0.17, 0.2) compositions have been prepared by the ceramic method (CE) and by several gel processing techniques: the colloidal method (CG), the gelatine method (GE), the citrate method (CI) and a polymeric route (PG). Fired samples have been evaluated as ceramic pigments following enameling with the powders in ceramic glazes. The results show that a yellow ceramic pigment is obtained in all samples without significative differences among the different methods and compositions. This yellow ceramic pigment has been identified as a Pr–(Ca–ZrO₂) solid solution.     

Synthesis, through pyrolysis of aerosols, of YIn1−xMnxO3 blue pigments and their efficiency for colouring glazes

Mn-doped YInO₃ blue pigments have been synthesised at a much lower temperature (1100 °C) than that required by the traditional solid state method (1400 °C). The developed procedure, which is based on the pyrolysis at 600 °C of aerosols generated from aqueous solutions of Y, In and Mn nitrates followed by an annealing treatment at 1100 °C, yields spherical pigments particles with heterogeneous size in the optimum range required for ceramic applications (<10 μm). The amount of Mn introduced in the YInO₃ matrix has been systematically varied in order to evaluate the effects of the Mn content on the colour properties of the pigments. It has been found that the optimum pigment composition (bluer colour with the lowest Mn content) is given by the formula YIn_0.90Mn_0.10O₃. The technological performance of these YIn_1−xMn_xO₃ blue pigments has also been evaluated by testing their efficiency for colouring ceramic glazes of different composition (boracic and plumbic) and properties, aiming to find a less toxic alternative for the Co-based pigments commonly used by the ceramic industry.     

Synthesis by pyrolysis of aerosols and ceramic application of Cr-doped CaYAlO4 red–orange pigments

The synthesis of red–orange Cr-doped YCaAlO₄ pigments has been improved (softer thermal conditions and lower environmental impact) and optimised by using the pyrolysis of aerosols method. We also study the crystallochemical features of the Cr chromophore with special emphasis on its oxidation state which has not been yet clarified, finding that Cr(III) and Cr(IV) species are present in the octahedral and interstitial tetrahedral sites of the YCaAlO₄ lattice, respectively. Finally, the applicability of this system as ceramic pigment was tested using conventional industrial glazes. A change from orange to pink shades was detected after glaze firing, which is mainly attributed to the Cr³⁺ to Cr⁴⁺ oxidation.     

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).     

尖晶石型无钴黑色陶瓷颜料的研究进展

黑色陶瓷颜料目前被广泛应用于陶瓷装饰领域,其传统制备工艺需加入氧化钴,但氧化钴的高价限制了黑色陶瓷颜料的发展,因此开发无钴黑色陶瓷颜料成为陶瓷颜料研究领域的热点之一,而尖晶石型无钴黑色陶瓷颜料因其出色的耐高温性、气氛适应性和化学稳定性受到众多研究者的青睐。本文基于尖晶石型无钴黑色陶瓷颜料的相关研究进展,围绕其呈色机理、制备原料种类和制备工艺等方面进行了详细的阐述与分析。目前,制备该类陶瓷颜料的原料主要分为化工原料、矿物原料和工业固废,制备工艺则主要包括传统高温固相法、微波焙烧法、化学沉淀法、溶胶-凝胶法、微乳液法、溶液燃烧法等,所制备颜料的呈色性能主要受原料组成中过渡金属元素之间摩尔比、焙烧温度和保温时间的影响。相较而言,采用微波焙烧工业固废制备该类陶瓷颜料具有良好的应用前景,但制备过程中尖晶石形成规律和演变机理以及工业固废所引入的杂质组分对颜料性能的影响还有待进一步研究。     

The interfacial and tribological properties of Ni–Cr alloy/ceramic tribo-couples under dry sliding contact

In this paper, the tribological behaviors of Ni–Cr alloy sliding against Si₃N₄ and WC–Co at 20 °C and 600 °C were investigated on a tribometer with a ball-on-disk configuration. The experimental results indicated that Ni–Cr alloy sliding against WC–Co exhibited higher wear resistance than that sliding against Si₃N₄. From the viewpoints of the interfacial interactions between metal and ceramic (chemical reaction, wetting, adhesion, transference), the wear mechanisms were elucidated. The tribological behaviors of Ni–Cr alloy/ceramic tribo-couples were well correlated with the interfacial characteristics, namely the reactive interface and the non-reactive interface. Ni–Cr alloy/Si₃N₄ tribo-couple showed severe adhesive wear as a result of the interfacial reaction between Ni and Si₃N₄, while the non-reactivity of Ni/WC interface is the most important factor corresponding to the moderate adhesive wear in Ni–Cr alloy sliding against WC–Co. Finally, the relations among the interfacial characteristics, wear behavior, and temperature were discussed. The results may provide some experimental evidences on the design and optimization of metal/ceramic tribo-couples.     

Assessment of gaseous,PM and trace element emissions from a 300-MW lignite-fired boiler unit for various fuel qualities

Modeling of effects of fuel quality on the emissions of major pollutants (NO_x, SO₂, CO₂ and PM) and eight trace elements (As, Co, Cr, La, Mo, Ni, Sb and U) from a 300-MW boiler unit fired with Thai lignite was the main focus of this study. The NO_x and SO₂ emission models were validated with the use of experimental data. Emission rates and specific emissions (per MW h) of the major pollutants and trace elements were quantified by including efficiencies of the flue gas desulphurization system and electrostatic precipitators in the computations. As shown in this work, the contributions of 300-MW boiler units fired with Thai lignite to the “greenhouse” and “acid rain” gas emissions in the region are significant. Additionally, substantial amounts of hazardous As, Cr and Ni are emitted from the boiler units into the atmosphere via fly ash particles.     

Encapsulated carbon black prepared by sol–gel-spraying: A new black ceramic pigment

As a new black ceramic pigment, encapsulated carbon black pigment has been prepared by a sol–gel-spraying method. The obtained pigment sintered at 900 °C for 2 h in air has a deep black hue (L* = 19), indicating carbon black can be fully covered. In the pigment, a dense coating layer on carbon black is formed due to the fast transformation from sol into gel by rapid extraction of solvent. The transparent silica phase spaces out the fine crystalline (zirconia or zircon), which permits to display the color of carbon black. This preparation method provides a way to prepare the encapsulated pigments. It will provide more colorful ceramic pigment applied in ceramic decoration by encapsulating.     

Cost-efficient,vivid and stable red hybrid pigments derived from naturally available sepiolite and halloysite

A series of clay/Fe₂O₃ red hybrid pigments with vivid color, good stability and low cost was synthesized via a facile one-step reaction of Fe(III) solution with sepiolite (Sep) or halloysite (HNTs). Sep or HNTs plays key roles to promote the in-situ transformation of Fe(III) into red hybrid pigments, because only black product was formed from Fe(III) in the absence of them. The addition of Sep and HNTs avoids the usage of any chemical precipitants, which is greatly superior to the traditional process. The a* coordinate values of the sepiolite/Fe₂O₃ (Sep/Fe₂O₃) and halloysite/Fe₂O₃ (HNTs/Fe₂O₃) hybrid pigments are 25.1 and 34.4, respectively, which indicate they have well red color performance. The positive influence of Sep or HNTs on the crystallization process and dispersion of Fe₂O₃ particles is responsible for the good red color. In addition, the hybrid pigments exhibit excellent stability to resist external attacks such as light, acid, alkaline, organic solvents and high temperature, and can be facilely spray-coated onto various substrates, e.g., glass, wood plate, ceramic plate, stone plate, and polyester plate, etc. Therefore, they are potential to be used as promising low-cost environment-friendly colorants in many fields such as ceramic, painting, coating, and printing.     

Production of a stable and homogeneous colloid dispersion of nano CoAl2O4 pigment for ceramic ink-jet ink

Different types of nano-CoAl₂O₄ pigments were prepared by controlling concentration of cetyltrimethylammonium bromide (CTAB) and polyvinyl pyrrolidone (PVP) as double capping agents in a co-precipitation process. The prepared nano-CoAl₂O₄ pigments were characterized by TGA, UV spectroscopy, and XRD. The optimum synthesized nano pigment was well dispersed into de-ionized water to form the ink. Rheology, surface tension and DLS of the prepared ink were examined. The prepared ink was printed onto a ceramic substrate. The printing process was repeated 1, 3 and 5 times in order to evaluate variations in the optical properties by changing thicknesses of the printed film. Appearance of the printed image and morphology of the prepared nano-pigments were observed by SEM. Moreover, shape and size of the nano-particles in the prepared ink were investigated by TEM. The obtained results revealed that the ink-jet printing method can be used to produce a nano-film of pigments on the ceramic.     

Cool and photocatalytic yellow ceramic pigments; from lead-tin to Cr doped scheelite pigments

The historical lead based pigments (XVII-XVIII century), the modern Ni,Sb-rutile (1939) and Pr-zircon (1961) yellow pigments as well as the novel yellow pigments based on Cr-scheelite and Mo-yttrium cerate pigments were synthesized and compared as semiconductors of high NIR reflectance (cool pigments) and with photocatalytic activity. All powders are wide band gap semiconductors (E_g=2.1–3.1?eV) with high NIR reflectance, ranging from 80% for Cr-Scheelite to 86% of Naples yellow, except Ni,Sb-rutile pigment that shows 55%. The low color performance of lead based pigments in alkyd paint and lead-free glazes along with its toxicity, discard these pigments as cool eco-friendly pigments. The Pr-zircon, Cr-scheelite and Mo-yttrium cerate pigments exhibit high NIR reflectance (R_NIR =?80–83%) and yellow coloration (b*?=?57.6–45.3) but only Pr-zircon and Cr-scheelite show color stability in alkyd paint and lead free glaze applications. Regarding to results of Orange II photodegradation test, lead based and Ni,Sb-rutile pigments inhibits the photolysis of the UV irradiation, acting as protecting agents from irradiation. The Mo-cerate shows a slight photocatalytic activity (t_1/2 =?301?min) and both Cr-scheelite and Pr-zircon pigments show a moderate activity (t_1/2 =?198 and 184?min respectively). Looking at a possible industrial application, the leaching test shows that the fluorides released by Pr-zircon (16.8?mg/g) as well as the Cr(VI) of Cr-scheelite (6?mg/g) should be treated and controlled. The Cr-scheelite solid solution Ca(Cr_xW_1-x)O₄ is stable to x?=?0.2 but its pigmenting capacity saturates at x?=?0.1.     

Facile non-aqueous synthesis of high color rendering C@ZrSiO4 encapsulation pigment with carbon-containing precursors as in-situ carbon sources

A zircon encapsulated carbon black (C@ZrSiO₄) pigment with high color rendering was synthesized via facile non-aqueous acetic acid (NAA) assisted sol-gel method using carbon-containing precursors (zirconium n-propoxide and tetraethoxysilane) as in-situ carbon sources. The effects of the NAA amount and heat treatment temperature on the structure and properties of the synthesized encapsulation pigments were characterized by XRD, FT-IR, FE-SEM, HR-TEM, EDS, XPS and CIELAB colorimeter, respectively. The results showed that the C@ZrSiO₄ encapsulated pigments heating at 1000?°C for 2?h in N₂ atmosphere presented a dense and stable encapsulation structure as well as deep dark hue when the mole ratio of NAA and Zr (NAA/Zr) was 3:1, and the chromaticity values were L*?= 21.20, a*?= 0.56, b*?= ?0.09 and C_ab =?0.57, respectively, which were contributed to the high homogeneity at atomic level in ZrSiO₄ sol and the tight bonding between carbon black carbonized by carbon containing group and zircon matrix. In addition, the pigment exhibited excellent chemical stability, thermal stability and tinctorial strength when it was used in water, acid, alkali, organic solvents and ceramic glaze. Especially, these pigments improved the utilization of raw materials and avoided the use of heavy metals or transition metals as coloring agent, which was an environment-friendly black ceramic pigment.