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.     

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.     

Solution combustion synthesis of FeCr2O4:Zn,Al pigment powders

FeCr₂O₄:Zn,Al pigment powders were prepared via a solution combustion synthesis method. Effects of Zn and Al dopants and less/extra Fe content on the structure, molecular bonds, and optical properties of powders were studied. Results showed that addition of dopants as well as extra/less content of Fe led to weaker combustion and consequently lower X-ray diffraction peak intensities, lattice parameters, and differential thermal analysis peak intensities. Moreover, Fourier transform infrared analysis illustrated that the band position of Cr–O and Fe–O bonds were shifted to higher frequencies with moving away from stoichiometry. In addition, scanning electron micrographs showed that in all samples, porous spongy microstructures were formed with highly flake-like agglomerated particles. Furthermore, there was a significant difference between the powder samples and the tiles colored with in glaze powders due to the partial dissolution of pigments in contact with the molten glaze of tiles. In comparison to the tile colored with the stoichiometric FeCr₂O₄ pigments without dopants, the color difference (ΔE) in the tiles colored by the iron chromite pigments doped with Zn and Al dopants and less/extra Fe content reached the high values as large as ΔE = 36.19. The solar reflectance values (R_s) in near-infrared region were above 50% in all samples. Near 80% R_s in the tile colored by the iron chromite pigment doped with 3 mol% Zn and the yellowish brown appearance (L* = 43.44, a* = 6.77, b* = 18.38, c* = 19.59, h = 69.79) showed that the sample was a good candidate for cool building materials such as roof tiles.     

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.     

A comparison of the effect of nanostructured MgCr2O4 and FeCr2O4 additions on the microstructure and mechanical properties of direct-bonded magnesia-chrome refractories

The effect on the microstructure and mechanical properties of direct-bonded magnesia-chrome refractories of additions of nanostructured MgCr₂O₄ and FeCr₂O₄ is reported. The nanostructured additives, synthesized by the citrate-nitrate route and calcined at several different temperatures, were characterized by XRD, BET and TEM. Additions of 0.5 and 1 wt % of these nanostructured oxides were made to magnesia-chrome refractories and calcined at 1650 ^OC in a shuttle kiln. Their microstructures were analyzed by SEM/EDX and their physical and mechanical properties (permanent linear change (PLC), bulk density, apparent porosity, cold crushing strength (CCS) and hot modulus of rupture (HMOR) were determined according to the respective DIN standards. The addition of the nanostructured oxides to the magnesia-chrome refractories facilitated the formation of secondary spinels, influencing the physical and mechanical properties. FeCr₂O₄ additions increased the size of the secondary spinel due to liquid phase formation in the presence of magnetite impurities in the FeCr₂O₄ nano-powder. The addition of nano-sized MgCr₂O₄ and FeCr₂O₄ to the base formulation of the refractory increased the CCS from 67.4 MPa to 82.8 MPa and 81.0 MPa respectively, while nano-sized MgCr₂O₄ increased the HMOR value from 5.48 MPa to 5.91 MPa and nano-sized FeCr₂O₄ increased the HMOR from 5.48 MPa to 5.72 MPa. This smaller increase than that obtained with FeCr₂O₄ additions is attributed to liquid phase formation in the presence of magnetite, as observed by XRD.     

Glycine–nitrate synthesis of Sr doped La2Zr2O7 pyrochlore powder

Abstract

Abstract

Materials with A₂B₂O₇ (pyrochlore) structure have received significant attention for their applications as new protonic conductors and materials used in electronic devices. One of the unique synthesis routes for La₂Zr₂O₇ (pyrochlore) powders is the glycine–nitrate combustion method, which shows superior properties of the synthesised powder using glycine as a complexing agent. The Sr doped La₂Zr₂O₇ powders in pure pyrochlore structure were produced using this approach. Selected characteristics of the synthesised powders, such as crystal structure, lattice parameters, crystallite size, the vibrational properties, the morphology of the particles, along with the specific surface area and particle size, have been investigated. The dependence of some properties on annealing temperatures of the powders has been studied.     

A comparative study on citrate sol-gel and combustion synthesis methods of CoAl2O4 spinel

CoAl₂O₄ spinel was successfully synthesized by combustion synthesis method using glycine and urea by 1:1 molar ratio as fuels and sol-gel process using citric acid as a chelating agent. The as-synthesized powders were calcined at desired temperatures to obtain CoAl₂O₄ spinel as a single phase. X-ray diffraction, thermogravimetric, and differential thermal analysis results revealed that the formation of CoAl₂O₄ spinel in combustion method needs 300°C higher temperatures than those of sol-gel. Scanning electron microscopy and transmission electron microscopy analysis results revealed that “sol-gel spinel” had nanometric particle size which was smaller than those of “combustion spinel.” Temperature programed reduction with hydrogen and Fourier transform infrared spectroscopy results declared that there was a little residual cobalt oxide in combustion spinel while there is no oxide resided in “sol-gel spinel.” Consequently, the sol-gel method has more benefit in synthesizing spinel with sulfate precursors than combustion.     

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.     

Synthesis and acetone gas sensing properties of Ag activated hollow sphere structured ZnFe2O4

Sheet stacked ZnFe₂O₄ hollow spheres have been synthesized through a simple hydrothermal method using Zn(CH₃COO)₂ and Fe(NO₃)₃ as Zn and Fe sources, respectively. Then a series of Ag activated ZnFe₂O₄ composites are prepared. XRD patterns demonstrate that the as-synthesized powders are pure ZnFe₂O₄. FE-SEM images exhibit that the as-synthesized Ag-ZnFe₂O₄ particles are spherical with the diameter of 800–1000?nm. TEM images demonstrate that the as-synthesized Ag-ZnFe₂O₄ are hollow sphere structure. The gas sensing tests show that 0.25?wt% Ag-ZnFe₂O₄ has the highest responses to 100?ppm acetone vapor at 175?°C, and response time and recovery time are 17 and 148?s respectively. In addition, 0.25?wt% Ag-ZnFe₂O₄ has a good selectivity to acetone. Ag activated ZnFe₂O₄ composites exhibit excellent acetone gas sensing properties and gives potential for the detection of acetone vapor in the application of practical industrial processes and health control.     

Effects of the preparation methods on the performance of the Cu–Cr–Fe/γ-Al2O3 catalysts for the synthesis of 2-methylpiperazine

Co-precipitation, impregnation and ultrasonic sol–gel (USG) methods have been used to prepare Cu–Cr–Fe/γ-Al₂O₃ catalysts, which were further used to synthesize 2-methylpiperazine. The catalysts were characterized by XRD, XPS, TG/DSC, BET, TPR, AAS and TEM. It is found that preparation method can greatly impact the catalytic performance of the catalysts, the Cu–Cr–Fe/γ-Al₂O₃ catalyst prepared by the ultrasonic sol–gel method proved to be the most active and stable for this reaction. The dispersion and stabilization of Cu⁰ in the reduced catalysts are attributed to the existence of CuCr₂O₄ and Fe₂O₃. A surprising copper migration was detected by XPS analysis for the Cu–Cr–Fe/γ-Al₂O₃-USG catalyst after the calcination process, which may be crucial to the high activity and stability of this catalyst.     

Properties of NiFe2O4 ceramics from powders obtained by auto-combustion synthesis with different fuels

Nickel ferrite (NiFe₂O₄) powders derived by auto-combustion synthesis using three different fuels (citric acid, glycine and dl-alanine) have been characterized. The sintering behavior of ceramics using these powders has been compared. Oxygen balance (OB) setting for the chemical reaction is found to regulate the combustion reaction rate. A rapid reaction rate and a high flame temperature are achieved with dl alanine fuel yielding single phase NiFe₂O₄ powder in the as-burnt stage, whereas powders derived with citric acid and glycine fuels show poor crystallinity and necessitate post-annealing. The powder particles are largely agglomerated with a non-uniform distribution in shape and size, and the average particle size is estimated in the range ~ 54–71 nm. Powders derived from dl-alanine fuel show better phase purity, smaller crystallite size, larger surface area and superior sintering behavior. Additional Raman modes discerned for dl-alanine derived powder support a 1:1 ordering of Ni²⁺ and Fe³⁺ at the octahedral sites relating to microscopic tetragonal P4₁22 symmetry expected theoretically for the formation of NiFe₂O₄ with inverse spinel structure. Microstructure of sintered ceramics depends on the precursor powders that are used and sintering at 1200 °C is found to be optimum. Citric acid and glycine derived powders yield high saturation magnetization (M_s~47–49 emu/g), but poor dielectric properties, whereas dl-alanine derived powders yield ceramics with high resistivity (~3.4×10⁸ Ω cm), low dielectric loss (tan δ~0.003 at 1 MHz) and high magnetization (46 emu/g). Dielectric dispersion and impedance analysis show good correlation with the changes in the ceramic microstructure.     

Understanding the solidification and leaching behavior of synthesized Cr-containing stainless steel slags with varying Al2O3/SiO2 mass ratios

This study investigated the effect of Al₂O₃/SiO₂ mass ratios on the equilibrium crystallization behavior of synthesized CaO–SiO₂–MgO–Al₂O₃–Cr₂O₃ stainless steel slags to understand the selective concentration behavior of Cr into a primary Mg(Cr,Al)₂O₄ spinel phase during slag solidification and to determine the leaching stability of Cr-containing slags. The spinel solid solution was precipitated within the temperature range of 1600-1400 °C, where the Cr/(Cr+Al) mole ratio in the Mg(Cr,Al)₂O₄ spinel phase gradually decreased for slags with higher Al₂O₃/SiO₂ mass ratios. When the Al₂O₃/SiO₂ mass ratio increased from 0.125 to 0.5, the Cr content in the amorphous glass phase gradually decreased, with a subsequent increase in the Cr content in the crystalline phase. For slags with a unit Al₂O₃/SiO₂ mass ratio and MgO mole percent comprising less than the combined sum of the Cr₂O₃ and Al₂O₃ mole percents, the Cr content in the amorphous glass phase increased, which was correlated with the enhanced substitution of Cr³⁺ with Al³⁺ in the spinel. The trend of the amount of Cr-related ions in the leachate was consistent with the trend of Cr in the amorphous glass phase: the amount decreased for slags with Al₂O₃/SiO₂ mass ratios from 0.125 to 5 and then increased for slags with an Al₂O₃/SiO₂ mass ratio of 1. The results suggest that the addition of appropriate amounts of Al₂O₃ to stainless steel slags could be conducive to stabilizing Cr into the primary spinel phase to minimize Cr leaching into the environment.     

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.     

Magnetic phase transition and magneto-dielectric analysis of spinel chromites: MCr2O4 (M = Fe,Co and Ni)

In this work, we present magnetic phase transition temperatures and magneto-dielectric coupling in MCr₂O₄ (M = Fe, Co and Ni) ceramics, synthesized using sol–gel auto-combustion route. In order to develop their respective crystalline textures, all these chromites were calcined at 650?°C for 2?h. X-ray diffraction patterns confirmed that FeCr₂O₄ had a rhombohedral structure while NiCr₂O₄ and CoCr₂O₄ exhibited a spinel-type cubic structure. The presence of relevant elements in the specific stoichiometric ratios was confirmed using energy dispersive X-ray spectroscopy. The shapes and sizes of the grains for all the samples were determined using the images obtained from a field emission scanning electron microscope. Temperature dependent magnetic analysis have shown that FeCr₂O₄, CoCr₂O₄ and NiCr₂O₄ are ferromagnetic at 5?K and their magnetic phase transition temperatures were measured as 80, 83 and 90?K, respectively. Spin-orbit interference was also studied through magneto-dielectric coupling for these chromites using a modified impedance analyzer set-up.     

Synthesis of non-agglomerating submicron/nano-Yb2Si2O7 powders by a carbon-coated coprecipitation method

We herein report a novel carbon-coated coprecipitation method to synthesize non-agglomerating submicron/nano-β-Yb₂Si₂O₇ powders. Yb(C₂H₃O₂)₃·4H₂O and silica sol (alkaline) were chosen as the ytterbium source and silicon source, respectively. A carbon surface layer is processed using sucrose as carbon source to hinder the contact and sintering of β-Yb₂Si₂O₇ particles during heat treatment under a protective atmosphere, and then the carbon layer could be completely removed by inletting air at 900°C during cooling process. The as-synthesized Yb₂Si₂O₇ powders demonstrate an average size of 271 nm with a narrow distribution of 142–531 nm. The results show that the carbon layer could successfully solve the severe agglomeration or sintering of nanometer β-Yb₂Si₂O₇ particles during the calcination process. The as-developed carbon-coated coprecipitation technique is an effective method to fabricate high purity submicron/nano-Yb₂Si₂O₇ powders.     

Effect of fuel type on the microstructure and magnetic properties of solution combusted Fe3O4 powders

Porous magnetite (Fe₃O₄) powders were synthesized by solution combustion method using the glycine and urea at different fuel to oxidant ratios (ϕ). The combustion behavior depended on the fuel type as characterized by thermal analysis. The structure and phase evolution investigated by X-ray diffraction method showed nearly single phase Fe₃O₄ powders which were achieved only by using the glycine fuel at ϕ=1. The specific surface area and porous structures of the as-combusted Fe₃O₄ powders were characterized by N₂ adsorption-desorption isotherms and scanning electron microscopy, respectively. The surface area using the glycine fuel (62.6 m²/g) was higher than that of urea fuel (42.5 m²/g), due to different combustion reactions. Magnetic properties of the as-combusted powders were studied by vibration sample magnetometry which exhibited the highest saturation magnetization of 74 emu/g using the glycine fuel at ϕ=1 on account of its high purity and large crystallite size.     

Color parameters of Y2Cu2O5 green-blue nanopigments fabricated by the sol-gel combustion method and their efficiency for coloring the glazed tiles

Non-toxic Y₂Cu₂O₅ nanopigments were synthesized by sol-gel combustion method and the effects of synthesis parameters on their chromatic properties have been studied. The chromatic properties of the samples were studied by UV-vis reflectance spectroscopy and the L^*a^*b^* coordinates were evaluated using the CIE Lab1976 color scales. The results showed that the chromatic properties of nanopigments were changed by altering the synthesis conditions such as pH and the molar ratio of the fuel to oxidizer. Also some Y₂Cu₂O₅ micro sized pigments were synthesized by solid state reaction and the measurements showed that the chromatic properties of the nanopigments were slightly bigger than those of the large particles indicating that the nanopigments were more stunning. Using DTA analysis it was found that the nanopigments were very stable in the temperature range of 50–950 °C. The measurements of a^* and b^* showed that the nanopigments are also very stable in glazes.     

Microwave dielectric properties of (1−x)ZnTa2O6−xMgNb2O6 ceramics

Single phase MgNb₂O₆ and ZnTa₂O₆ powders were synthesized by solid-state method, and the high quality factor composite ceramics of (1?x)ZnTa₂O₆?xMgNb₂O₆ (x=0, 0.05, 0.10, 0.15, 0.20, 0.25 and 1.0) were prepared using the as-synthesized powders. The microwave dielectric properties, microstructure, phase transition and sintering behavior of the composite ceramics were investigated. The X-ray diffraction analysis revealed that solid solution between ZnTa₂O₆ and MgNb₂O₆ phases appeared in the composite ceramic. SEM results show that the grain sizes of the composite ceramics increased with increasing x values. The temperature coefficient of resonant frequency of (1?x)ZnTa₂O₆?xMgNb₂O₆ composite ceramics reaches near-zero of 1.02 ppm/°C with ε_r=35.58 and a high quality factor of 65500 GHz when x=0.20 and sintered at 1350 °C for 2 h.     

Coupled Experimental and Thermodynamic Optimization of the Na2O–FeO–Fe2O3–Al2O3 System: Part 1. Phase Diagram Experiments

As part of the complete thermodynamic modeling of the Na₂O–FeO–Fe₂O₃–Al₂O₃ system, the Na₂O–FeO–Fe₂O₃–Al₂O₃ phase diagrams in air (1583 and 1698 K) and at Fe saturation (1573 and 1673 K) were investigated using the quenching method followed by Electron Probe Micro‐Analyzer (EPMA) and X‐ray Diffraction (XRD) phase analysis. General features of the phase diagrams in this system were well revealed for the first time. A complete meta‐oxide solid solution between NaAlO₂ and NaFeO₂ was observed. An extensive solid solution of Na₂(Al,Fe)₁₂O₁₉ Na‐β?‐alumina was found and the existence of a miscibility gap in this solution was confirmed. Several compatibility triangles of three‐phase assemblages were also identified in air and at Fe saturation.     

Fabrication and characterizations of Cr3+-doped ZnGa2O4 transparent ceramics with persistent luminescence

0.5 at.% Cr:ZnGa₂O₄ precursor was synthesized by the co-precipitation method with nitrates as raw materials, using ammonium carbonate as the precipitant. Low-agglomerated Cr:ZnGa₂O₄ powders with an average particle size of 43 nm were obtained by calcining the precursor at 900℃ for 4 h. Using the powders as starting materials, 0.5 at.% Cr:ZnGa₂O₄ ceramics with an average grain size of about 515 nm were prepared by presintering at 1150℃ for 5 h in air and HIP post-treatment at 1100℃ for 3 h under 200 MPa Ar. The in-line transmittance of 0.5 at.% Cr:ZnGa₂O₄ ceramics with a thickness of 1.3 mm reaches 59.5% at the wavelength of 700 nm. The Cr:ZnGa₂O₄ ceramics can be effectively excited by visible light and produce persistent luminescence at 700 nm. For Cr:ZnGa₂O₄ transparent ceramics, the brightness of afterglow was larger than 0.32 mcd/m² after 30 min, which is far superior to that of Cr:ZnGa₂O₄ persistent luminescence powders.