Sol–gel synthesis and phase composition of ultrafine ceria-doped zirconia powders for functional ceramics

Ultrafine ceria-doped zirconia powders with the general formula Ce_xZr_1?xO₂ oriented for functional ceramic materials for different purposes were prepared by modified sol–gel synthesis with use of monoethanolamine or tetraethylammonium hydroxide. All powders were high crystallized single-phase systems with average crystallite size 8–11 nm. It was established that doping of zirconia by ceria led to a decrease in the crystallite size. At the same time the nature of the zirconium salt anion has little effect on crystallite size. However, only powders obtained from zirconyl chloride had crystallites with sizes below 10 nm. When x = 0.150–0.155, a sharp increase in the crystallite size was observed regardless of the used organic components. Use of tetraethylammonium hydroxide resulted in formation of Ce_xZr_1?xO₂ crystallites of 2–3 nm smaller than that which was obtained in the presence of monoethanolamine.     

The influence of reactive milling on the structure and magnetic properties of nanocrystalline MnFe2O4

Nanocrystalline manganese ferrites (MnFe₂O₄) have been synthesized by direct milling of metallic manganese (Mn) and iron (Fe) powders in distilled water (H₂O). In order to overcome the limitation of wet milling, dry milling procedure has also been utilized to reduce crystallite size. The effects of milling time on the formation and crystallite size of wet milled MnFe₂O₄ nanoparticles have been investigated. It has been observed that single phase 18.4 nm nanocrystalline MnFe₂O₄ is obtained after 24 h milling at 400 rpm. Further milling caused deformation of the structure as well as increased crystallite size. With the aim of reducing the crystallite size of 18.4 nm, MnFe₂O₄ sample dry milling has been implemented for 2 and 4 h at 300 rpm. As a result, the crystallite size has been reduced to 12.4 and 8.7 nm, respectively. Effects of the crystalline sizes on magnetic properties were also investigated. Magnetization results clearly demonstrated that crystallite size has much more effect on the magnetic properties than average particle size.     

Synthesis and characterization of nanometric gadolinia powders by room temperature solid-state displacement reaction and low temperature calcination

Nanometric-sized gadolinia (Gd₂O₃) powders were obtained by applying solid-state displacement reaction at room temperature and low temperature calcination. The XRD analysis revealed that the room temperature product was gadolinium hydroxide, Gd(OH)₃. In order to induce crystallization of Gd₂O₃, the subsequent calcination at 600 ∼ 1200 °C of the room temperature reaction products was studied. Calculation of average crystallite size (D) as well as separation of the effect of crystallite size and strain of nanocrystals was performed on the basic of Williamson-Hall plots. The morphologies of powders calcined at different temperatures were followed by scanning electron microscopy. The pure cubic Gd₂O₃ phase was made at 600 °C which converted to monoclinic Gd₂O₃ phase between 1400° and 1600 °C. High-density (96% of theoretical density) ceramic pellet free of any additives was obtained after pressureless sintering at 1600 °C for 4 h in air, using calcined powder at 600 °C.     

Effects of SiO2 addition on TiO2 crystal structure and photocatalytic activity

A series of TiO₂–SiO₂ mixtures – having the following stoichiometry Ti_1?xSi_xO₂, with x = 0, 0.1, 0.3 and 0.5 atoms per formula unit – were prepared by using precursor oxides and fired at three temperatures (900, 1000 and 1200 °C). The modifications in the structure and, consequently, on the photocatalytic activity, induced by the addition of SiO₂ into the TiO₂ powder, were thoroughly investigated by using various analytical techniques: X-ray powder diffraction, electron microscopy (FE-SEM and TEM), XPS, FT-IR, DRS and BET analysis. The results underlined as essentially no solid solution occurs between the two crystalline end-members. Nevertheless, silica addition caused a retarding effect on anatase-to-rutile phase transformation and on the crystallite growth.The photocatalytic activity of the powders was assessed in gas phase and the results were explained by taking into account the anatase and rutile relative amounts in the samples, their crystallite size, the surface hydroxyl groups adsorbed on the photocatalysts and the surface area of the mixtures.     

Nanocrystaline solid solution CeO2–Bi2O3

Nanocrystalline powders of solid solution CeO₂–Bi₂O₃ were synthesized by self-propagating room temperature reaction (SPRT) procedure with composition (Ce_1?xBi_xO_2?δ where the x = 0.1–0.5). X-ray diffraction analyses show that for x < 0.50 a solid solution with fluorite structure is formed. Rietveld's structure refinement method was applied to characterize prepared powders and its microstructure (size–strain). The lattice parameters increase according to Vegard's rule with increasing of Bi concentration. The average crystallite size is about 2–3 nm. Spectroscopic ellipsometry and Raman scattering measurements were used to characterize the samples at room temperature. The Raman measurements demonstrated electron molecular vibrational coupling and increase of oxygen vacancy concentration whereas increase of Bi content provokes a small decrease of optical absorption edge in comparison with pure ceria. Specific surface area of obtained powders was measured by Brunauer–Emmet–Teller (BET) method.     

Colored films produced by electron beam deposition from nanometric TiO2 and Al2O3 pigment powders obtained by modified polymeric precursor method

Synthesis and the characterization of TiO₂:5%Co (green), TiO₃:5%Fe (brown-reddish), TiO₂:2%Cr (brown), Al₂O₃:5%Co (blue), Al₂O₃:5%Fe (brown-reddish) and Al₂O₃:2%Cr (light green) nanometric pigment powders using polymeric precursor (modified Pechini's method) is reported. Colored thick films were deposited on amorphous quartz substrates by electron beam physical vapor deposition (EB-PVD) using pellets of the pigment powders as target. The evaporation process was carried out in vacuum of 4 × 10⁻⁶ Torr and the amorphous quartz substrates were kept at 350 °C during deposition. The TiO₂-based pigment powders presented crystalline anatase phase and the Al₂O₃-based pigment powders showed corundum phase, investigated by X-ray diffraction (XRD). The average particle size of the pigment powders was about 20 nm, measured by scanning electron microscopy with field emission gun (SEM-FEG). Diffuse reflectance spectra and colorimetric coordinates L¹, a¹, b¹ using the CIE-L¹a¹b¹ method are shown for the pigment powders, in the 350–750 nm range. The colored thick films were characterized by transmittance (UV–Vis) and atomic force microscopy (AFM). The average film roughness was ∼5.5 nm and the average grain size obtained in the films was around 75 nm. Films with thickness from 400 nm to 690 nm were obtained, measured by talystep profiler. Transmission spectra envelop method has been used to obtain refractive index and thickness of the Al₂O₃ colored thick films.     

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.     

Synthesis of nanocrystalline Mg0.6Cd0.4Fe2O4 ferrite by glycine-nitrate auto-combustion method and investigation of its microstructure and magnetic properties

Nanocrystalline Mg_0.6Cd_0.4Fe₂O₄ ferrite powders were produced by the glycine-nitrate auto-combustion method for the first time. The influence of the different molar ratios of glycine-to-nitrate G.N⁻¹) on the characteristics of the prepared powders was systematically investigated by X-ray diffraction (XRD), inductively coupled plasma optical emission spectroscopy (ICP-OES), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), field-emission scanning electron microscopy (FE-SEM) and vibrating sample magnetometry (VSM). Thermodynamic calculations revealed that the adiabatic flame temperature changes from 598.79 K to 1757.97 K by increasing the G.N⁻¹ ratios from 0.30 to 0.85. The results confirmed that under fuel-lean combustion (G.N⁻¹ = 0.30), Mg_0.6Cd_0.4Fe₂O₄ nanoparticles can be obtained at a significantly lower temperature and shorter synthesis time, compared to other preparation methods like standard ceramic and co-precipitation. The XRD and ICP results showed that the crystallite size of the powders changes in the range of 8–43 nm, and their Cd content notably decreases with increasing the G.N⁻¹ values. The FE-SEM results proved that the porosity and size of the as-prepared ferrite nanoparticles drastically change with variations in the G.N⁻¹ ratio. The evolution of phase, crystallite/particle size, and magnetic properties after annealing was discussed in detail. At the optimized annealing condition, the synthesized Mg_0.6Cd_0.4Fe₂O₄ ferrite offered a high saturation magnetization of 41.70 Am² kg⁻¹ and a coercivity of 1.92 kA m⁻¹, indicating noticeably better soft magnetic properties compared to the same ferrite produced by the other wet chemical methods.     

Poly(N-isopropylacrylamide) assisted microwave synthesis of magnesium aluminate spinel oxide for production of highly transparent films by hot compression

Magnesium aluminate spinel oxides have been prepared via poly(N-isopropylacrylamide) assisted microwave technique. The prepared MgAl₂O₄ powders showed a crystalline cubic structure with spinel phase after calcination at 600 °C only. The poly(N-isopropylacrylamide) amount showed a high effect on the crystallite size and the densification behavior of MgAl₂O₄. The increase of the amount of poly(N-isopropylacrylamide) reduced the sintering temperature of MgAl₂O₄ from 1400 °C to 1050 °C. The hot-pressed of MgAl₂O₄ powders in the presence of 3 wt% of poly(N-isopropylacrylamide) exhibited a full density at sintering temperature 1100 °C in 15 min only. The sintered films showed high transparency (81 ± 2%) in the wavelength range 500–1000 nm.     

Bismuth titanates candidates for high permittivity LTCC

Bi₂O₃–TiO₂ composites are known to possess attractive microwave dielectric properties. However, producing LTCC analogues with equally promising dielectric properties is problematic. Here, we show that judicious choice of both TiO₂ starting powders and dopants can produce composites with excellent properties. Three TiO₂ powders were evaluated: 1 μm-anatase, 1 μm-rutile and a nanosized (30 nm) mixture of 75–25 anatase-rutile. The best dielectric properties were obtained by using uncalcined nanosized anatase/rutile with Bi₂O₃ powder. By doping this Bi₂O₃–TiO₂ powder mixture with 0.112 wt.% CuO dielectric properties of Q × f = 9000 GHz, ɛ_r = 80 and τ_f = 0 ppm/K (at 300 K) were obtained at a sintering temperature of 915 °C.     

Solid-state synthesis and spark plasma sintering of submicron BaYxZr1 − xO3 − x/2 (x = 0, 0.08 and 0.16) ceramics

Fine powders (particle size of 100–200 nm) of BaY_xZr_1 − xO_3 − x/2 (x = 0, 0.08, 0.16) were produced by solid-state reaction at 1000–1050 °C using nanocrystalline ZrO₂ and BaCO₃ raw materials. The powders were densified by means of the spark plasma sintering process resulting in dense and homogeneous submicron microstructures. Near full density ceramics with grain size < 300 nm were obtained by sintering at 1600 °C for 1–5 min.     

Synthesis,characterization and sinterablity of 10 mol% Sm2O3-doped CeO2 nanopowders via carbonate precipitation

A carbonate coprecipitation method has been used for the facile synthesis of highly reactive 10 mol% Sm₂O₃-doped CeO₂ (20SDC) nanopowders, employing nitrates as the starting salts and ammonium hydrogen carbonate (AHC) as the precipitant. The AHC/RE³⁺ (RE = Ce + Sm) molar ratio (R) and the reaction temperature (T) affect significantly the final yield and precursor properties, including chemical composition and particle morphology. Suitable processing conditions are T = 60 °C and R = 5.0–10, under which precipitation is complete and the resultant precursors show ultrafine particle size, spherical particle shape, and good dispersion. Thus, the processed precursors are rare-earth carbonates with an approximate formula of Ce_0.8Sm_0.2(CO₃)_1.5·1.8H₂O, which directly yield oxide solid-solutions upon thermal decomposition at a low temperature of ∼440 °C. The 20SDC solid solution powders calcined at 700 °C show excellent reactivity and have been densified to ∼99% of the theoretical via pressureless sintering at a very low temperature of 1200 °C for 4 h.     

Effect of synthesis parameters on the size of cobalt ferrite crystallite

Nanoparticles of cobalt ferrite (CoFe₂O₄) were synthesized by the EDTA/Citrate complexing method and hydrothermal method without addition of surfactant. The influence of the pH of the reaction medium (8, 9 or 10), the temperature of the thermal treatment (600 °C, 800 °C or 1000 °C for the EDTA/Citrate method, and 120 °C, 140 °C or 160 °C for the hydrothermal method), and the duration of the thermal treatment (2, 4 or 6 h for the EDTA/Citrate complexing method, and 6, 15 or 24 h for the hydrothermal method) on the average crystallite size was studied by means of an experimental design based on the results obtained by XRD. Statistical analysis led to quantification of the influence of the synthesis parameters on the crystallite size of the powders. Results showed that the pH of the reaction medium is the parameter that shows the greatest influence on the growth of the crystallites of the powders obtained by the hydrothermal method, while calcination temperature is the most significant one for the powders produced by the EDTA/Citrate complexing method.     

Chromium substituted copper ferrites via gluconate precursor route

CuFe_2−xCr_xO₄ spinel (0≤x≤2) powders were synthesized by a soft chemistry method—the gluconate multimetallic complex precursor route. The complex precursors were characterized by elemental chemical analysis, infrared (IR) and ultraviolet–visible (UV–vis) spectroscopy, thermal analysis and Mössbauer spectroscopy. The oxide powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), IR, Raman and Mössbauer spectroscopy. It was shown that the structure, morphology and magnetic properties of the obtained spinel powders depend on the concentration of Cr³⁺ ion. The XRD of the chromium substituted copper ferrite powders calcined at 700 °C/1 h indicated the formation of a cubic spinel type structure for x=0.5, 1.0 and a tetragonal structure for x=0, 0.2, 2. The crystallite size ranged from 19 nm to 39 nm. The Mössbauer spectroscopy revealed the site occupancy of iron ions, relative abundance and internal hyperfine magnetic fields in both tetrahedral and cubic CuFe_2−xCr_xO₄ spinels.     

Synthesis and electrical properties of co-doping with La3+, Nd3+, Y3+, and Eu3+ citric acid-nitrate prepared samarium-doped ceria ceramics

Fluorite oxides Ce_0.8Sm_0.1Ln_0.1O_1.9 (denoted as SDC for singular doping and LnSDC for Ln=La, Nd, Y and Eu), were prepared by the citric acid–nitrate combustion reaction to act as electrolytes for intermediate-temperature solid oxide fuel cells (IT-SOFC). The thermal decomposition, phase identification, morphology, density, particle size distribution and electrical properties of the samples were studied by TGA/TDA, XRD, SEM, the Archimedes method, a laser size analyzer and Impedance spectroscopy, respectively. All crystallite powders that calcined at 800 °C had a cubic fluorite structure; the average crystallite size was between 63 and 68.5 nm. The pellets were then sintered at 1400 °C in air for 7 h. The relative densities of these pellets were over 95%, which was in good agreement with the results of the SEM. The impedance measurements were performed in an open circuit using two electrode configurations. The results showed that Ce_0.8Sm_0.1La_0.1O_1.9 had the highest electrical conductivity, σ_700 °C, equal to 6.59×10^?2 S cm^?1 and the lowest activation energy equal to 0.85 eV. It was therefore concluded that co-doping with the appropriate rare-earth cations can further improve the electrical properties of ceria electrolytes.     

Fabrication of Lu2O3:Eu transparent ceramics using powder consisting of mono-dispersed spheres

Mono-dispersed spherical Lu₂O₃:Eu (5 mol%) powders for transparent ceramics fabrication were synthesized by urea-based homogeneous precipitation technique. The effects of the doped-Eu³⁺ on the synthesis of Lu₂O₃:Eu particles were investigated in detail. The results show that the doping of Eu³⁺ ions into Lu system can significantly decrease the particle size of the resultant precursor spheres. Owing to the sequential precipitation in Lu/Eu system, there are compositional gradients within each of the resultant precursor spheres. Well dispersed, homogeneous and spherical/near spherical Lu₂O₃:Eu powders were obtained after calcination at 600–1000 °C for 4 h. The powder calcined at 600 °C shows better sintering behavior and can be densified into transparent ceramic after vacuum sintering at 1700 °C for 5 h. The luminescence properties of the obtained Lu₂O₃:Eu powder and transparent ceramic were also studied.     

Multiferroic bismuth manganite prepared by mechanochemical synthesis

Multiferroic bismuth manganite (BiMnO₃) is known as a material that exhibits both ferromagnetic and ferroelectric properties making it interesting for various technological applications. Unfortunately, preparation of BiMnO₃ is not possible by a conventional solid-state reaction and it can form only from mixture of oxides at high pressures (>40 kbar).In this work single-phased BiMnO₃ was prepared for the first time by mechanochemical synthesis in a planetary ball mill. A mixture of Bi₂O₃ and Mn₂O₃ was intensively milled in air atmosphere, using stainless steel vials and balls. According to analysis of XPRD results BiMnO₃ obtained after milling for 240 min has a tetragonal structure with lattice parameters a = 3.9230 Å, c = 3.920 Å and a crystallite size of 16.8 nm. The cumulative energy introduced into the system during milling for 240 min was 401 kJ/g. It was found that the obtained powders were agglomerated. Corresponding agglomeration factors were calculated from the results of BET and particle size distribution analysis.     

Synthesis,calcination and characterization of Nanosized ceria powders by self-propagating room temperature method

Nanometric ceria powders with fluorite-type structure were obtained by applying self-propagating room temperature method. The obtained powders were subsequently thermally treated (calcined) at different temperatures for different times. Powder properties such as specific surface area, crystallite size, particle size and lattice parameter have been studied. Roentgen diffraction analysis (XRD), BET and Raman scattering measurements were used to characterize the as-obtained (uncalcined) powder as well as powders calcined at different temperatures.It was found that the average diameter of the as-obtained crystallites is in the range of 3–5 nm whereas the specific surface area is about 70 m²/g. The subsequent, 15 min long, calcination of as-obtained powder at different temperatures gradually increased crystallite size up to ～60 nm and reduced specific surface down to 6 m²/g. Raman spectra of synthesized CeO_2?y depicts a strong red shift of active triply degenerate F_2 g mode as well as additional peak at 600 cm^?1. The frequency of F_2 g mode increased while its line width decreased with an increase in calcination temperature. Such a behavior is considered to be the result of particle size increase and agglomeration during the calcination. After the heat treatment at 800 °C crystallite size reached value larger than 50 nm. Second order Raman mode, which originates from intrinsic oxygen vacancies, disappeared after calcination.     

Hydrothermal synthesis,magnetic properties and characterization of CoFe2O4 nanocrystals

Magnetic cobalt ferrite (CoFe₂O₄) nanocrystals were synthesized via the hydrothermal method and the crystallite size was measured using Sherrer's equation. Instrumental broadening was a significant parameter for determining crystallite size. The effect of annealing time and calcination on crystallite size and magnetic properties was discussed. It was found that the coercivity was highly dependent on the crystallite size. As the crystallite size increased from 61 to 68.2 nm, room temperature coercivity increased from 1488 Oe to 1700 Oe, while high coercivity (5.2 kOe) was achieved at lower temperature (80 K). It was found that the presence of hematite could affect the crystallite size after calcination.     

Chemical oxidation of residual carbon from ZnAl2O4 powders prepared by combustion synthesis

The removal of carbon residue from ZnAl₂O₄ nanopowders by annealing at 500–800 °C leads to a decrease of specific surface area from 228.1 m²/g to 47.6 m²/g. At the same time, the average crystallite size increased from 5.1 nm to 14.9 nm. In order to overcome these drawbacks, a new solution for removing the carbon residue has been suggested: chemical oxidation using hydrogen peroxide. In terms of carbon removal, a H₂O₂ treatment for 8 h at 107 °C proved to be equivalent to a heat treatment of 1 h at 600 °C. The benefits of chemical oxidation over thermal oxidation were obvious. The specific surface area was much larger (188.1 m²/g) in the case of the powder treated with H₂O₂. The average crystallite size (5.8 nm) of ZnAl₂O₄ powder treated with H₂O₂ was smaller than the crystallite size (8.2 nm) of the ZnAl₂O₄ powder annealed at 600 °C.