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.     

Solution combustion of spinel CuMn2O4 ceramic pigments for thickness sensitive spectrally selective (TSSS) paint coatings

A series of spinel-type CuMn₂O₄ ceramic pigments were prepared by a facile and low-cost sol-gel solution combustion method and used as cost-effective materials to fabricate thickness sensitive spectrally selective (TSSS) paint coatings by a convenient spray-coating technique. The chemical component, crystalline morphology, and optical property of the copper manganese oxide ceramic pigment could be accurately controlled by altering the annealing temperature. X-ray diffraction (XRD) analysis confirmed that the ceramic pigments annealed at 500 °C for 1 h coincided well with the XRD patterns of crystalline CuMn₂O₄ in the JCPDS database, and there were segregated phases of CuO and Mn₂O₃. Furthermore, the pure spinel CuMn₂O₄ phase could be achieved at 900 °C for 1 h. The copper manganese oxide ceramic pigments could serve as an effective pigment for fabricating the TSSS paint coating, and the TSSS paint coatings based on ceramic pigments calcined at 900 °C showed solar absorptance of 0.895–0.905 and thermal emittance of 0.186–0.310. In addition, the accelerated thermal stability test revealed that the TSSS paint coating exhibited good thermal stability when it was exposed to air at a temperature of 300 °C for 300 h. Hence, the fabricated TSSS paint coating could be used as a solar absorber coating in the low-to-mid temperature domain.     

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.     

Co-doped willemite ceramic pigments: Technological behaviour,crystal structure and optical properties

Cobalt-doped willemite is a promising blue ceramic pigment, but some important aspects concerning crystal structure, optical properties and technological behaviour are still undisclosed. In order to get new insight on these features, willemite pigments (Zn_2?xCo_xSiO₄, 0 < x < 0.3) were synthesized by the ceramic route and characterized from the structural (XRPD with Rietveld refinement), optical (DRS and colorimetry), microstructural (SEM, STEM, TEM, EDX, EELS) and technological (simulation of the ceramic process) viewpoints. The incorporation of cobalt in the willemite lattice, taking preferentially place in the Zn1 tetrahedral site, induces an increase of unit-cell parameters, metal–oxygen distances, and inter-tetrahedral tilting. It causes shifting and enhanced splitting of spin-allowed bands of Co²⁺ in tetrahedral coordination, implying slight changes of crystal field strength Dq and Racah B parameter, but increasing spin-orbit coupling parameter λ. Willemite pigments impart deep blue hue to ceramic glazes and glassy coatings with a colouring performance better than commercial Co-bearing colorants in the 800–1200 °C range. Detailed SEM-TEM investigation and microanalysis proved that no diffusion phenomena occur at the pigment–glassy coating interface and that willemite pigments are chemically inert during firing at 1050 °C.     

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.     

Hidden value in low-cost inorganic pigments as potentially valuable magnetic materials

Inorganic pigments are substances that develop colour in organic solids such as ceramics and glazes, and are usually a complex mixture of oxides, and relatively low-cost. Their chromatic properties have been extensively studied, yet surprisingly the magnetic and electrical properties of these economic and common materials have been neglected, despite the fact many are based on ferrite spinels. Therefore, we investigated these properties in commercial black and brown pigments, to assess their potential as magnetic materials. The brown and black pigments were found to be spinel ferrites, with estimated formulas of Fe_1.34Cr_0.62Mn_0.66Zn_0.22Ni_0.10Co_0.06O₄ and Fe_1.02Cr_0.97Co_0.57Mn_0.23Ni_0.21O₄, respectively. The brown pigment also contained a higher amount of SiO₂ compared to the black pigment (~7 mol% vs. ~2 mol%), which appeared as a second phase of crystalline quartz, and adversely affected its porosity, magnetisation and electrical ac conductivity, compared to the black pigment. However, both were very magnetic and very soft ferrites. The brown pigment had M_s=11.7 A m² kg⁻¹ and H_c of 1.5 kA m⁻¹, with a high electrical conductivity (σ) of 4×10⁻⁴−7×10⁻³ Ω⁻¹ m⁻¹ between 100 Hz and 1 MHz. The black pigment was equally magnetically soft, but had a much greater magnetisation and lower electrical conductivity, with M_s=18.7 A m² kg⁻¹, H_c=2.4 kA m⁻¹, and σ=5×10⁻⁶−8×10⁻⁵ Ω⁻¹ m⁻¹ between 100 Hz and 1 MHz.This work has revealed the potential hidden value of low-cost commercial inorganic pigments based on spinel ferrites as magnetic materials. This demonstrates their potential at low-cost alternative materials for applications such as in power supply transformers, switching materials and sensors, where soft magnetisation is especially important.     

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.     

Metallurgy dusts as a pigment for glazes and engobes

This study is focused on using the dust from metallurgy as a pigment. The agglomerating dust is formed during metallurgical processes. This waste product is interesting for recycling process. The main mineralogical phase of dust is hematite α-Fe₂O₃. Both synthetic and natural iron oxides are commonly used as pigments in ceramic industry. In this experiment the metallurgy dusts were used as a pigment for preparation of glazes and engobes. Agglomerating dusts were used both precalcined thermally at 700 °C and 900 °C and in an original state. The prepared glazes were composed of a transparent glaze base with 10 wt% agglomerating dusts as pigment. The glazes calcined at 1060 °C were finally yellow colored and glazes calcined at 900 °C were brown colored. Engobes contained a ceramic clay base with 1, 5, 10 and 50 wt% of dust as pigment. Engobes calcined at 900 °C were red and grey colored. The pigments were characterized by X-ray diffraction (XRD), chemical (XRFS) analysis, granulometry (PSD), thermogravimetric (TG) and differential thermal (DTA) analysis, scanning electron microscopy (SEM) and CIELab values.     

Blue-violet ceramic pigments based on Co and Mg Co2−xMgxP2O7 diphosphates

Solid solutions of Co and Mg diphosphates with compositions Co_2?xMg_xP₂O₇ (x = 0, 0.1, 0.2, 0.3, 0.5, 0.7, 1.0, 1.5 and 1.8) have been prepared and characterized for the first time as alternative low-toxicity blue ceramic pigments. The compositions were prepared through the conventional coprecipitation route and calcined up to 1000 °C/2 h. Samples were characterized by thermal analysis, XRD, SEM/EDX, UV–vis-NIR spectroscopy and colour measurements (CIE-L^*a^*b^*). Isostructural Co_2?xMg_xP₂O₇ diphosphate solid solutions (monoclinic system and P21/c spatial group) formed successfully within the studied range of compositions, accompanied only by a minor quantity of residual Co or Mg orthophosphates (M₃(PO₄)₂). Interestingly, the obtained solid solutions developed nice blue-violet colourations even with high Mg doping after enamelling within double-firing (x = 1.5–1.8) and single-firing (x = 1.0–1.5) ceramic glasses. These optimal compositions containing a minimized Co amount (measured values around 7–16 wt%) could be therefore less toxic alternatives to the conventional Co₃(PO₄)₂ blue ceramic pigment.     

Preparation and characterization of porous MgAl2O4 spinel ceramic supports from bauxite and magnesite

Porous magnesium aluminate spinel (MgAl₂O₄) ceramic supports were fabricated by reactive sintering from low-cost bauxite and magnesite at different temperatures ranging from 1100 to 1400 °C and their sintering behavior and phase evolution were evaluated. The effects of sintering temperature on the pore structure, size and distribution as well as on the main properties of spinel ceramic supports such as flexural strength, nitrogen permeation flux and chemical resistance were investigated. The supports prepared at 1300 °C showed a homogeneous pore structure with the average pore size of 4.42 μm, and exhibited high flexural strength (35.6 MPa), high gas permeability (with nitrogen gas flux of 3057 m³ m⁻² h⁻¹ under a trans-membrane pressure of 0.1 MPa) and excellent chemical resistance.     

Production of brown pigments for porcelain insulator applications

In this study, production of brown pigment for the ceramic insulator applications by using inexpensive natural raw materials or waste materials was undertaken. Different pigment compositions were designed, synthesised and examined. As a source of chromium, chromite, Cr₂O₃ and ferrochrome were used. Limonite, grinding waste, flotation waste and iron oxide scale were used as an iron source whereas manganese oxide and ferromanganese were used as a manganese source. The colour of glazed insulator bodies change from dark brown to light brown depending on the pigment composition. The pigments prepared with ferrochrome, manganese oxide, flotation waste (C6) or iron oxide scale (D4) and calcined at 1300 °C have a darker brown colour and possess suitable L*a*b* values as 30.1, 2.7, 1.6 for C6 and 30.9, 2.1, 0.3 for D4, which are closer to the L*a*b* values (30.1, 2.9, 0.1) of commercial MnFeCr pigments. The results indicate that waste materials containing iron can be used to produce brown pigments to be used in the insulator application in ceramic industry and as a result of this waste material can be converted into a value-added product. Also, ferrochrome can be used successfully as chromium source and help to reduce the cost of the pigment.     

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.     

Blue pigments based on CoxZn1−xAl2O4 spinels synthesized by the polymeric precursor method

The Co_xZn_1?xAl₂O₄ system (x = 0; 0.1; 0.3; 0.5; 0.7; 0.9 and 1) was synthesized by the polymeric precursor method and characterized by the techniques XRD, TG-DTA, IR, UV–vis and colorimetry. The XRD patterns displayed the characteristic peaks of the spinel structure and a good crystallinity. The DTA curves showed an exothermic peak corresponding to the enthalpy of the transition taking place at about 700 °C. The infrared spectra displayed vibrations at about 650, 550, 540, 520, 500, 490 cm^?1, which were ascribed to the spinel structure. The UV–vis spectra presented three bands at 550, 580 and 620 nm attributed to the Co²⁺ spin transitions in tetrahedral sites. The colorimetric data point out the formation of blue pigments, corresponding to highly negative values of b¹. The lightness, coordinate L¹, increases with the heat treatment temperature. These facts reveal that Co_xZn_1?xAl₂O₄ is a promising system that can be employed to obtain ceramic blue pigments.     

Microwave sintered sol–gel derived BaTiO3 and Ba0.95La0.05TiO3 ceramic samples for capacitor applications

Sol–gel derived BaTiO₃ and Ba_0.95La_0.05TiO₃ powders were calcined at 700 °C for 40 min and sintered at 1100 °C for 1 h in a microwave furnace to obtain single-phase perovskite ceramic samples. About 98% of the theoretical density was obtained in the sintered BT ceramic samples. Room temperature (RT) dielectric constant (ε_r) and dielectric loss (tan δ) at 1 kHz frequency of the BLT ceramic samples were found to be ~2220 and 0.005, respectively. High value of ε_r, low value of tan δ and negligible temperature coefficient of capacitance from RT to 60 °C suggested the suitability of BLT ceramic samples for multi-layer capacitor applications.     

Nickel aluminate spinel formation during sintering of simulated Ni-laden sludge and kaolinite

Incorporating Ni-laden waste sludge into kaolinite-based construction ceramic materials appears promising based on the identified nickel bearing phases, evaluated incorporation efficiency and nickel leachability of the products. Nickel aluminate spinel (NiAl₂O₄) results from sintering kaolinite and nickel oxide between 990 and 1480 °C, with more than 90% incorporation efficiency achieved at 1250 °C and 3 h sintering. At lower temperature (990 °C), NiAl₂O₄ formed from the reaction between nickel oxide and the defect spinel generated from the kaolinite–mullite reaction series. In addition to sintering temperature and time, four raw material mixing procedures were employed, and the ball-milled slurry samples had the highest nickel incorporation efficiency. Prolonged leach testing of NiO, NiAl₂O₄ and the product from sintered kaolinite + NiO mixtures was carried out using the TCLP extraction fluid #1 (pH 4.9) to evaluate the product stability, and the results revealed the superiority of spinel products over NiO in stabilizing nickel.     

A novel low-firing microwave dielectric ceramic Li2ZnGe3O8 with cubic spinel structure

A Li₂ZnGe₃O₈ ceramic was investigated as a promising microwave dielectric material for low-temperature co-fired ceramics applications. Li₂ZnGe₃O₈ ceramic was prepared via the conventional solid-state method. X-ray diffraction data shows that Li₂ZnGe₃O₈ ceramic crystallized into a cubic spinel structure with a space group of P4₁32. Dense ceramic with a relative densities of 96.3% were obtained when sintered at 945 °C for 4 h and exhibited the optimum microwave properties with a relative permittivity (ε_r) of 10.3, a quality factor (Q × f) of 47,400 GHz (at 13.3 GHz), and a temperature coefficient of resonance frequency (τ_f) of −63.9 ppm/°C. The large negative τ_f of Li₂ZnGe₃O₈ ceramic could be compensated by rutile TiO₂, and 0.9Li₂ZnGe₃O₈–0.1TiO₂0·1TiO₂ ceramic sintered at 950 °C for 4 h exhibited improved microwave dielectric properties with a near-zero τ_f of −1.6 ppm/°C along with ε_r of 11.3 and a Q × f of 35,800 GHz (11.6 GHz). Moreover, Li₂ZnGe₃O₈ was found to be chemically compatible with silver electrode when sintered at 945 °C.     

In situ synthesis of orange rutile ceramic pigments by non-conventional methods

Different precursor-mixtures of orange Cr,Sb-TiO₂ ceramic pigment have been obtained by non-conventional methods (heterogeneous ammonia coprecipitation, urea homogeneous coprecipitation, PECHINI polyester method and an original aqueous–organic coprecipitation method in water–diethylenglycol medium) in order to produce in situ the pigment through the ceramic body firing. The pigmenting performances of powders were appraised in two cases: (a) as ceramic pigment for glazed porcelain stoneware and (b) as ceramic inks for screen printing of porcelain stoneware. Samples were characterised by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), UV–vis-NIR spectroscopy by diffuse reflectance method, CIE-L*a*b* colour parameters, BET specific surface area and crystallite size measured by the Scherrer method. The colouring performance of raw powders obtained by non-conventional methods in glazed porcelain stoneware improves that of the ceramic samples fired at 1100 °C used as reference. TEM observations indicate nanostructured powders with pigmenting performance depending on factors such as their specific surface area (BET), the crystalline phases detected by XRD (e.g. anatase–rutile presence) and their crystallite size (Scherrer measurements). Ammonia coprecipitated samples, both in water and in water–diethylenglycol medium without surfactant addition, or modified by the addition of sodium dodecyl sulphate as surfactant, stand out by their colouring performance.     

Study of Cr-SnO2 ceramic pigment and of Ti/Sn ratio on formation and coloration of these materials

In this study, Cr_xSn_1−xO₂ (0 ≤ x ≤ 0.06) and Cr_0.03Sn_0.97−yTi_yO₂ (0 < y ≤ 0.97) compositions were synthesized by the ceramic method and characterized by X-ray diffraction, UV–vis spectroscopy and CIE L*a*b* (Commission Internationale de l’Eclairage L*a*b*) parameters measurements. From Cr_xSn_1−xO₂ samples fired at 1600 °C/1 h, x = 0.03 was established as the composition limit of formation of solid solutions. When x ≤ 0.01, better coloration of glazed tiles were obtained from short thermal treatment (1400 °C/1 h or 1600 °C/1 h) than from long thermal treatment (1400 °C/24 h). When 0.01 < x < 0.06 small variations of color in glazed tiles were obtained from samples fired at 1400 °C/24 h and 1600 °C/1 h. From Cr_0.03Sn_0.97−yTi_yO₂ compositions, a better purple color was obtained when y = 0.02 (Ti/Sn ∼ 2.1 × 10⁻²) than when y = 0.     

Brown ceramic pigments based on chromium(III)-doped titanite obtained by spray pyrolysis

Cr-doped titanite (CaTiSiO₅) pigments were synthesized through spray pyrolysis of aerosols generated from aqueous solutions containing colloidal silica, calcium chloride, titanium(IV) oxychloride and chromium(III) nitrate. This process yielded amorphous powders with spherical morphology and broad size distribution (<10 μm) after thermal decomposition at 600 °C. The titanite phase was obtained by further calcination at 800 °C without any addition of flux agents. The brown color of the pigments can be attributed mainly to the existence of Cr(IV) ions occupying both, octahedral positions of Ti(IV) and tetrahedral position of Si(IV), together with a small amount of Cr(III) present as Cr₂O₃. The optimum pigment obtained by this method corresponded to a Cr/titanite mole ratio of 0.04.     

Highest UV–vis transparency of MgAl2O4 spinel ceramics prepared by hot pressing with LiF

Reaction sintering of MgO and Al₂O₃ with addition of LiF as sintering additive was used to prepare MgAl₂O₄ spinel ceramic by hot pressing. The process parameter (temperature, pressure, dwell time), the stoichiometric ratio of MgO to Al₂O₃ and the selection of the alumina raw powder are equally important for highest transparency of the spinel ceramic. With this optimization highest transparency of 86% in the visible range at λ = 640 nm together with UV transmission of 62% at 200 nm for spinel ceramic with 4 mm thickness was reached.