Synthesis and study of a new class of red pigments based on perovskite YAlO3 structure

A red pigment has been prepared by substituting chromium ions in aluminum ion sites in YAlO₃ perovskite structure. In a first step, effect of various mineralizers on YAlO₃ formation has been investigated, which resulted in decrease of formation temperature down to 1400 °C. In the next step, a red pigment corresponding to YAl_1−yCr_yO₃ (y = 0.05), has been prepared by heating a mixture containing Y₂O₃, Al₂O₃ and Cr₂O₃ at 1500 °C for 6 h. Later, effect of the doped chromium amount on the pigment redness (a^*) has been studied. The highest redness has been obtained when y was 0.04(YAl_1−yCr_yO₃). Application of the prepared red pigment in low and high temperature glazes, demonstrated its high chemical and thermal stability.     

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.     

Solubility of blue CoAl2O4 ceramic pigments in water and diethylene glycol media

The chemical stability of blue CoAl₂O₄ ceramic pigment in aqueous and non-aqueous suspension was investigated. Distilled water and diethylene glycol (DEG) were used as media. The isoelectric points (IEP) for the commercial and synthesised CoAl₂O₄ pigment were determined to be 4.9 and 8.5, respectively. The IEP shifts toward acidic pH values for the commercial pigment with respect to the synthesised pigment due to the existence of the quartz phase. In water, the cobalt ion concentration was low (2.5 mg dm⁻³), and this concentration did not change with time. However, the aluminium ion concentration was initially high and then decreased to ∼10 mg dm⁻³ at pH 9 and 11 due to the precipitation of Al³⁺ ions as an Al(OH)₃ phase. In DEG, the dissolution of pigment particles with higher ion concentrations (>800 mg dm⁻³) was more significant than that of the aqueous medium, implying that CoAl₂O₄ pigment has insufficient chemical stability in DEG medium with respect to aqueous suspensions.     

Synthetic optimization of Li[Ni1/3Co1/3Mn1/3]O2 via co-precipitation

Li[Ni_1/3Co_1/3Mn_1/3]O₂ powders were synthesized from co-precipitated spherical metal hydroxide, (Ni_1/3Co_1/3Mn_1/3)(OH)₂. The preparation of metal hydroxide was significantly dependent on synthetic conditions, such as pH, amount of chelating agent, stirring speed, etc. The optimized condition resulted in (Ni_1/3Co_1/3Mn_1/3)(OH)₂, of which the particle size distribution was uniform and the particle shape was spherical, as observed by scanning electron microscopy. Calcination of the uniform metal hydroxide with LiOH at higher temperature led to a well-ordered layer-structured Li[Ni_1/3Co_1/3Mn_1/3]O₂, as confirmed by Rietveld refinement of X-ray diffraction pattern. Due to the homogeneity of the metal hydroxide, (Ni_1/3Co_1/3Mn_1/3)(OH)₂, the final product, Li[Ni_1/3Co_1/3Mn_1/3]O₂, was also significantly uniform, i.e., the average particle size was of about 10 μm in diameter and the distribution was relatively narrow. As a result, the corresponding tap-density was also high approximately 2.39 g cm−3, of which the value is comparable to that of commercialized LiCoO₂. In the voltage range of 2.8-4.3, 2.8-4.4, and 2.8-4.5 V, the discharge capacities of Li[Ni_1/3Co_1/3Mn_1/3]O₂ electrode were 159, 168, and 177 mAh g⁻¹, respectively. For elevated temperature operation (55 °C), the resulted capacity was of about 168 mAh g⁻¹ with an excellent cyclability.     

Crystallization kinetics of lanthanum monoaluminate (LaAlO3) nanopowders prepared by co-precipitation process

Lanthanum monoaluminate (LaAlO₃) nanopowders were synthesized using La(NO₃)₃·6H₂O and Al(NO₃)₃·6H₂O as starting materials by a co-precipitation method. The crystallization kinetics of the LaAlO₃ nanopowders has been investigated by using differential thermal analysis (DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and selected area electron diffraction (SAED). The XRD results and SAED patterns show that the rhombohedral LaAlO₃ nanopowders have been obtained when the precipitates as calcined at 1092 K for 10 min. The activation energy for the crystallization of the rhombohedral LaAlO₃ nanopowders is determined as 286.75 kJ/mol by a non-isothermal method. The TEM examination shows that the rhombohedral LaAlO₃ has a spherical morphology with the size ranging from 30 to 50 nm.     

Synthesis optimization of Li1 + x[Mn0.45Co0.40Ni0.15]O2 with different spherical sizes via co-precipitation

Li_1 + x[Mn_0.45Co_0.40Ni_0.15]O₂ spherical cathode materials with different sizes (about 2 and 5 μm) were fabricated by calcining uniform spherical metal carbonate, [Mn_0.45Co_0.40Ni_0.15]CO₃ with lithium hydroxide at high temperature. The precursor of spherical metal carbonate, [Mn_0.45Co_0.40Ni_0.15]CO₃, was obtained via co-precipitation method at room temperature, which was significantly dependent on synthetic conditions, such as the reaction temperature, the concentration of NH₄HCO₃, and stirring speed, etc. The optimized condition resulted in [Mn_0.45Co_0.40Ni_0.15]CO₃, of which the particle size distribution was uniform and the particle shape was spherical. The final products, Li_1 + x[Mn_0.45Co_0.40Ni_0.15]O₂, had a well-ordered layered structure and uniform homogeneity. Raman spectroscopy analysis showed the Raman-active species E_g and A_1g modes were observed at 488, 473 cm^− 1 and 597, 590 cm^− 1, respectively, for the obtained spherical cathode materials.     

Synthesis of CoAl2O4/Al2O3 nanoparticles for ceramic blue pigments

The demand for pigments for industrial ceramic ink-jet printing is increasing steadily. The main challenge is the availability of ceramic pigments comprised of small-sized particles in order to avoid clogging of the printer head nozzle. This work presents a novel way to prepare ceramic blue pigment as a shell/core structure of CoAl₂O₄/Al₂O₃ nanoparticles through a simple and low-cost process. In this process, the colour tone of nano-pigment can be tuned by the selection of the cobalt precursor/Al₂O₃ ratio and calcining temperature.     

Synthesis of CeAlO3/CeO2-Al2O3 for use as a solid oxide fuel cell functional anode material

A composite electrocatalyst was developed to be fitted for the purpose of satisfying the features required for use as a solid oxide fuel cell functional anode material. The main functionality searched for was the ability to make the direct oxidation of carbon containing fuels in an SOFC without being severely coked. The present paper deals with the synthesis and characterization of such material. Therefore, ceramic electrocatalysts composed of CeAlO₃, CeO₂ and Al₂O₃ were synthesized by the amorphous citrate method and calcined at temperatures ranging from 300 °C to 900 °C. The synthesis procedures were designed to produce nanometric sized powders for which the calcination conditions were selected in order to fulfill requirements such as ease to be sintered; formation of selected phases upon calcinations at different temperatures; particle size control; surface area and morphology well suited for the production of ceramic suspensions to be processed into an SOFC functional anode. The main results have shown that increasing the calcination temperature under an oxidizing atmosphere induces the CeAlO₃ phase with a tetragonal perovskite type structure to undergo a phase transformation to CeO₂ (and Al₂O₃) with cubic fluorite type structure. However, the structure is able to be reversed and reduced back to the CeAlO₃ phase if calcined under a hydrogen atmosphere. The increase in the calcination temperature increases the particle average size, reduces the surface area and increases the material density, considering the same phase and crystalline structure. It was shown that the synthesis and calcinations procedures hinder the crystallographic identification of the presence of alumina.     

Structural investigation and dielectric studies on Mn substituted Pb(Zr0.65Ti0.35)O3 perovskite ceramics

Polycrystalline samples of manganese substituted lead zirconium titanate (PZMT) with general formula Pb(Zr_0.65−xMn_xTi_0.35)O₃ ceramics have been synthesised by high temperature solid state reaction technique. X-ray diffraction (XRD) patterns were recorded at room temperature to study the crystal structure employing Rietveld technique. All the patterns could be refined to R3c space group with rhombohedral symmetry. Bond lengths and angles have been calculated from refined parameters. Microstructural properties of the materials were analysed by scanning electron microscope (SEM) and compositional analysis were carried out by energy dispersive spectrum (EDS) measurements. All the materials exhibit ferroelectric to paraelectric transition. The Curie temperature (T_c) increases with the Mn concentration. We have observed that dielectric constant decreases and AC conductivity increases with the frequency. The correlation between lattice parameters and T_c for the present samples has been observed.     

Effect of fluorine in the preparation of Li(Ni1/3Co1/3Mn1/3)O2 via hydroxide co-precipitation

Uniform and spherical Li(Ni_1/3Co_1/3Mn_1/3)O_(2−δ)F_δ powders were synthesized via NH₃ and F⁻ coordination hydroxide co-precipitation. The effect of F⁻ coordination agent on the morphology, structure and electrochemical properties of the Li(Ni_1/3Co_1/3Mn_1/3)O_(2−δ)F_δ were studied. The morphology, size, and distribution of (Ni_1/3Co_1/3Mn_1/3)(OH)_(2−δ)F_δ particle diameter were improved in a shorter reaction time through the addition of F⁻. The study suggested that the added F improves the layered characteristics of the lattice and the cyclic performance of Li(Ni_1/3Co_1/3Mn_1/3)O₂ in the voltage range of 2.8-4.6 V. The initial capacity of the Li(Ni_1/3Co_1/3Mn_1/3)O_1.96F_0.04 was 178 mAh g⁻¹, the maximum capacity was 186 mAh g⁻¹ and the capacity after 50 cycles was 179 mAh g⁻¹ in the voltage range of 2.8-4.6 V.     

Particle size effect of Li[Ni0.5Mn0.5]O2 prepared by co-precipitation

Spherical (Ni_0.5Mn_0.5)(OH)₂ with different secondary particle size (3 μm, 10 μm in diameter) was synthesized by co-precipitation method. Mixture of the prepared hydroxide and lithium hydroxide was calcined at 950 °C for 20 h in air. X-ray diffraction patterns revealed that the prepared material had a typical layered structure with space group. Spherical morphologies with mono-dispersed powders were observed by scanning electron microscopy. It was found that the layered Li[Ni_0.5Mn_0.5]O₂ delivered an initial discharge capacity of 148 mAh g⁻¹ (3.0-4.3 V) though the particle sizes were different. Li[Ni_0.5Mn_0.5]O₂ having smaller particle size (3 μm) showed improved area specific impedance due to the reduced Li⁺ diffusion path, compared with that of Li[Ni_0.5Mn_0.5]O₂ possessing larger particle size (10 μm). Although the Li[Ni_0.5Mn_0.5]O₂ (3 μm) was electrochemically delithiated to Li_0.39[Ni_0.5Mn_0.5]O₂, the resulting exothermic onset temperature was around 295 °C, of which the value is significantly higher than that of highly delithiated Li_1−δCoO₂ (∼180 °C).     

Enhancement of the dielectric,piezoelectric, and ferroelectric properties in BiYbO3-modified (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3 lead-free ceramics

Lead-free (1−x)(Ba_0.85Ca_0.15)(Ti_0.9Zr_0.1)O₃−xBiYbO₃ [(1−x)BCTZ−xBYO] piezoelectric ceramics in the range of BYO concentrations were prepared by the conventional oxide-mixed method, and the effect of BYO content on their microstructure, crystalline structure, density and electrical properties was investigated. A dense microstructure with large grain was obtained for the ceramics with the addition of BYO. The ceramics with x=0.1% exhibit an optimum electrical behavior of d₃₃~580 pC/N, r~10.9 Ω, k_p~56.4%, and tan δ~1.12% when sintered at a low temperature of ~1350 °C. When the measuring electric field is 40 kV/cm, the well-saturated and square-like P–E loops for the ceramics were observed with P_r~12.2 μC/cm² and E_c~1.83 kV/cm.     

Dielectric properties of CuO-doped La2.98/3Ba0.01(Mg0.5Sn0.5)O3 ceramics at microwave frequency

The microwave dielectric properties of La_2.98/3Ba_0.01(Mg_0.5Sn_0.5)O₃ ceramics prepared by the conventional solid-state method were investigated for application in mobile communication. A 100 °C reduction of the sintering temperature was obtained by using CuO as a sintering aid. A dielectric constant of 20.0, a quality factor (Q × f) of 50,100 GHz and a temperature coefficient of resonant frequency τ_f of −78.3 ppm/°C were obtained when La_2.98/3Ba_0.01(Mg_0.5Sn_0.5)O₃ ceramics with 0.25 wt.% CuO were sintered at 1500 °C for 4 h.     

Effect of synthesis condition on the structure and electrochemical properties of Li[Ni1/3Mn1/3Co1/3]O2 prepared by hydroxide co-precipitation method

The layered Li[Ni_1/3Co_1/3Mn_1/3]O₂ powder with good crystalline and spherical shape was prepared by hydroxide co-precipitation method. The effects of pH value, NH₄OH amount, calcination temperature and extra Li amount on the morphology, structure and electrochemical properties of the cathode material were investigated in detail. SEM results indicate that pH value affected both the morphology and the property of the cathode material, and the highest discharge capacity in the first cycle of 163 mAh g⁻¹ (2.8-4.3 V) was obtained at pH value was 12. On the contrary, the NH₄OH amount, which was used as a chelating agent, only affected the particle size distribution of the material. The calcination temperatures caused great difference in the structure and property of layered Li[Ni_1/3Co_1/3Mn_1/3]O₂, and the best electrochemical properties were obtained at the calcination temperature of 800 °C. Extra Li amount not only caused difference in the material structure, but also affected their electrochemical properties. With increasing Li amount, the lattice parameters (a and c) increased monotonously, and the highest first cycle coulombic efficiency (the ratio of discharge capacity to charge capacity in the first cycle) was obtained with the Li/M of 1.10. Therefore, the optimum synthetic conditions for the hydroxide co-precipitation reaction were: pH value was 12, NH₄OH amount was 0.36 mol L⁻¹, calcination temperature was 800 °C and the Li/M molar ratio was 1.10.     

Effect of MnO2 addition on the structure and electric properties of (Ba0.94Ca0.06)(Ti0.9Sn0.1)O3 ceramics

The (Ba_0.94Ca_0.06)(Ti_0.9Sn_0.1)O₃ (BCTS) ceramics with pure perovskite structure were prepared by conventional solid-state reaction route with the addition of 0–0.8?mol% MnO₂. The crystal structure, microstructure, and electric properties were investigated systematically. X-ray diffraction patterns showed that the addition of MnO₂ changed the ratio of the coexistence of orthorhombic and tetragonal phases, which had apparent influences on the piezoelectric properties of ceramics. When the addition amount is 0.2?mol%, the average grain size increases from ~41.88–52.24?µm, and, however, the average grain size decreases with further addition > 0.2?mol%. A good combination of properties and performance could be achieved with the addition of 0.4?mol% MnO₂. The mechanical quality factor Q_m, dielectric loss tanδ, piezoelectric constant d₃₃, and planar electromechanical coefficient k_p measured are 216, 0.011, 578?pC/N, and 0.39, respectively. Therefore, results of this study suggest that the BCTS-Mn ceramics synthesized could exhibit a great potential for piezoelectric component applications.     

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.     

Preparation and characterization of Cr2O3-TiO2-Al2O3-V2O5 green pigment

Green pigments with high near infrared reflectance based on a Cr₂O₃-TiO₂-Al₂O₃-V₂O₅ composition have been synthesized. Cr₂O₃ was used as the host component and mixtures of TiO₂, Al₂O₃ and V₂O₅ were used as the guest components. TiO₂, Al₂O₃, and V₂O₅ were mixed into 39 different compositions. The spectral reflectance and the distribution of pigment powder were determined using a spectrophotometer and a scanning electron microscope, respectively. It was found that a pigment powder sample S9 with a Cr₂O₃-TiO₂-Al₂O₃-V₂O₅ composition of 80, 4, 14 and 2 wt%, respectively, gives a maximum near infrared solar reflectance of 82.8% compared with 49.0% for pure Cr₂O₃. The dispersion of pigment powders in a ceramic glaze was also studied. The results show that the pigment powder sample S9 is suitable for use as a coating material for ceramic-based roofs.     

Direct decomposition of NO into N2 and O2 on BaMnO3-based perovskite oxides

Effects of dopant in BaMnO₃ perovskite oxide on the NO direct decomposition activity were investigated. NO direct decomposition activity was greatly elevated by doping La and Mg for Ba and Mn site in BaMnO₃, respectively. The highest N₂ yield was achieved on Ba_0.8La_0.2Mn_0.8Mg_0.2O₃. The NO decomposition rate increased with increasing NO partial pressure with P_NO^1.19. Coexistence of oxygen lowered the N₂ yield with P_O2^−0.18; however, N₂ yield of 40% was sustained even under coexisting of 5% O₂ at 1123 K. Adsorption state of oxygen was also studied with temperature programmed desorption (TPD) method and the desorption temperature of oxygen was lowered by doping Mg for Mn site in BaMnO₃.     

Enhanced electrochemical performance of nano-sized LiFePO4/C synthesized by an ultrasonic-assisted co-precipitation method

A simple and effective method, the ultrasonic-assisted co-precipitation method, was employed to synthesize nano-sized LiFePO₄/C. A glucose solution was used as the carbon source to produce in situ carbon to improve the conductivity of LiFePO₄. Ultrasonic irradiation was adopted to control the size and homogenize the LiFePO₄/C particles. The sample was characterized by X-ray powder diffraction, field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). FE-SEM and TEM show that the as-prepared sample has a reduced particle size with a uniform size distribution, which is around 50 nm. A uniform amorphous carbon layer with a thickness of about 4-6 nm on the particle surface was observed, as shown in the HRTEM image. The electrochemical performance was demonstrated by the charge-discharge test and electrochemical impedance spectra measurements. The results indicate that the nano-sized LiFePO₄/C presents enhanced discharge capacities (159, 147 and 135 mAh g⁻¹ at 0.1, 0.5 and 2 C-rate, respectively) and stable cycling performance. This study offers a simple method to design and synthesis nano-sized cathode materials for lithium-ion batteries.     

Fabrication and characterization of (Pb(Mg1/3Nb2/3)O3, Pb(Yb1/2Nb1/2)O3, PbTiO3) ternary system ceramics

New ternary compositions in the Pb(Mg_1/3Nb_2/3)O₃-Pb(Yb_1/2Nb_1/2)O₃–PbTiO₃ (PMN-PYbN-PT) system were prepared using 0.5Pb(Yb_1/2Nb_1/2)O₃-0.5PbTiO₃ (PYbNT) and (1-x)Pb(Mg_1/3Nb_2/3)O₃–xPbTiO₃ (x = 0.26; PMNT26 or x = 0.325; PMNT32.5) powders synthesized via the columbite method. Dense (≥ 96% of theoretical density) ceramics with PMN/PYbN mole ratios of 25/75 (R-25), 50/50 (R-50) and 75/25 (R-75T and R-75R) were fabricated by reactive sintering at 1000 °C for 4 h. Therefore, incorporation of PYbNT to PMNT successfully decreased sintering temperature of PMNT from 1200 °C-1250 °C to 1000 °C. Samples with higher density and perovskite ratio together with lower weight loss possessed higher dielectric and piezoelectric values in each composition. The R-75 samples had remanent polarization (P_r) values of 34-36 μC/cm² and piezoelectric charge coefficient (d₃₃) of 560 pC/N. The sharp phase transition PMNT as a function of temperature became broader or more diffuse with increasing PYbNT content. However, PYbNT addition to PMNT increased Curie temperature (T_c) from 183 °C (for PMNT32.5) to 220-242 °C (for R-75T and R-75R) to 336 °C (for R-25). Therefore, these ternary compositions can be tailored for various high temperature applications due to the relatively higher T_c with enhanced piezoelectric and dielectric properties as compared to PMNT.