Red ceramic pigments of terbium-doped ceria prepared through classical and non-conventional coprecipitation routes

Reddish ceramic pigments based on cerianite compositions Ce_1−xTb_xO₂ (x = 0.1, 0.2 and 0.3) and Ce_0.9Tb_0.05Y_0.05O₂ have been prepared. Firstly, the optimal composition giving the best red colour was selected (Ce_0.9Tb_0.1O₂) from ceramic and chlorides coprecipitation samples fired at 1100–1500 °C. Secondly, the effect of using different classical and non-conventional coprecipitation routes on the synthesis and colouring performance of CeO₂-Tb red pigments was analyzed for the first time. In addition to classical coprecipitation we tested also the use of hydrothermal treatment and other more homogeneous coprecipitation methods with oxalates and urea. Homogeneous coprecipitation was also combined with ultrasonic or microwave irradiation. Samples were characterized by thermal analysis, XRD, SEM/EDX, optical spectroscopy and colour measurements. Interestingly, the optimization of synthesis methods enabled to obtain more homogeneous (single phase) CeO₂-Tb solid solutions at lower temperatures (400–1100 °C), exhibiting very nice reddish colourations associated to lower energy bandgaps (E_g below 2.30 eV). The obtained optimal compositions could be therefore alternative candidates as environmentally friendly reddish ceramic pigments.     

Creep behaviour of alumina/YAG composites prepared by different sintering routes

Al₂O₃-5 vol.% Y₃Al₅O₁₂ (YAG) composite powders have been prepared by surface doping of α-alumina powders by an yttrium chloride aqueous solution. Two commercial, one submicron-sized, the other ultra-fine, alumina powders were compared as matrix materials. YAG phase was yielded by an in situ reaction promoted by the subsequent thermal treatment of the doped powders. In particular, a flash soaking into a tubular furnace kept at a fixed temperature in the range 1050-1150 °C was employed, for inducing the crystallization of yttrium-aluminates on the alumina particles surface, but avoiding a relevant crystallites growth. After that, aqueous suspensions of the calcined powders were dispersed by ball-milling and cast into porous moulds or simply dried in a oven. Slip cast green bodies were densified by pressure-less sintering, while powdered samples were consolidated by hot pressing or spark plasma sintering. The low- and high-temperature mechanical performances of the sintered materials were investigated and related to monolithic aluminas behaviour as well as to the composites microstructures. It is shown that the hot-pressed and spark plasma sintered composites present a significantly lower creep rate as compared to reference, monolithic alumina samples.     

Effect of freeze-drying treatment on the optical properties of SPS-sintered alumina

This study looks at the influence of alumina powder processing on the preparation of transparent alumina by Spark Plasma Sintering (SPS). Zeta potential measurements were carried out on alumina suspensions in order to determine the best dispersion conditions. Stable slurries were submitted to a spray freeze drying process and their sintering behavior was compared with the corresponding non spray freeze dried powders. Transparent alumina samples were successfully prepared from alumina powders by Spark Plasma Sintering. An optical model considering pore and grain size distributions has been developed to obtain information about porosity in dense materials. It was found that the final density and, accordingly, the optical properties were improved when spray freeze dried starting powder was used.     

Microstructure and optical properties of nanocrystalline Cu2O thin films prepared by electrodeposition

Cuprous oxide (Cu₂O) thin films were prepared by using electrodeposition technique at different applied potentials (−0.1, −0.3, −0.5, −0.7, and −0.9 V) and were annealed in vacuum at a temperature of 100°C for 1 h. Microstructure and optical properties of these films have been investigated by X-ray diffractometer (XRD), field-emission scanning electron microscope (SEM), UV-visible (vis) spectrophotometer, and fluorescence spectrophotometer. The morphology of these films varies obviously at different applied potentials. Analyses from these characterizations have confirmed that these films are composed of regular, well-faceted, polyhedral crystallites. UV–vis absorption spectra measurements have shown apparent shift in optical band gap from 1.69 to 2.03 eV as the applied potential becomes more cathodic. The emission of FL spectra at 603 nm may be assigned as the near band-edge emission.     

Structure characterization and mechanical properties of CeO2–ZrO2 solid solution system

The measured and calculated lattice parameters, microstructures, and mechanical properties (fracture toughness and microhardness) of CeO₂–ZrO₂ system ceramics are investigated, using CeO₂–ZrO₂ solid solution powder prepared by a microwave-induced combustion process. The CeO₂–ZrO₂ solid solution ceramics were sintered at 1500 °C for 6 h in air; the density of all specimens was greater than 94% of the theoretical density. For Ce_1−xZr_xO₂ (0.00  x  0.50), the measured lattice parameter is in accordance with that of Kim's doped CeO₂ model_. On the other hand, for x  0.50, the measured values fit Kim's doped ZrO₂ model. The fracture toughness and microhardness of CeO₂–ZrO₂ system ceramics with various compositions were investigated with Vickers indentation. The results showed that the crack mode of CeO₂–ZrO₂ solid solution was Palmqvist cracks under loads of 1 kg. Generally, the fracture toughness should increase with grain size at the submicron scale. However, larger grains may lead to spontaneous transformation, which should decrease the potential toughening at room temperature. This behavior was observed in the Ce_0.25Zr_0.75O₂ ceramic, which demonstrated a high fracture toughness that may be ascribed to two causes: (1) fine grain size and (2) transformation toughening.     

XPS and optical studies of different morphologies of ZnO nanostructures prepared by microwave methods

Zinc oxide (ZnO) nanostructures of various morphologies were prepared using a microwave-assisted aqueous solution method. Herein, a comparative study between three different morphologies of ZnO nanostructures, namely nanoparticles (NPs), nanoflowers (NFs) and nanorods (NRs) has been reviewed and presented. The morphologies of the prepared powders have been studied using field effect scanning electron microscopy (FESEM). X-ray diffraction (XRD) results prove that ZnO nanorods have biggest crystallite size compared with nanoflowers and nanoparticles. The texture coefficient (T_c) of three morphologies has been calculated. The T_c changed with varying morphology. A comparative study of surfaces of NPs, NFs and NRs were investigated using X-ray photoelectron spectroscopy (XPS). The possible growth mechanisms of ZnO NPs, NFs and NRs have been described. The optical properties of the ZnO nanostructures of various morphologies have been investigated and showed that the biggest crystallite size of ZnO nanostructures has lowest band gap energy. The obtained results are in agreement with experimental and theoretical data of other researchers.     

Influence of N2/Ar gas mixture ratio and annealing on optical properties of SiCBN thin films prepared by rf sputtering

Optical properties of amorphous thin films of silicon carbon boron nitride (Si–C–B–N) obtained by reactive sputtering has been studied. Compositional variations were obtained by changing the nitrogen and argon gas mixture ratio in the sputtering ambient. The effect of gas ratios and annealing on the optical properties was investigated. It was found that the transmittance of the films increases with nitrogen incorporation. Annealing at higher temperatures leads to considerable increase in transmittance. Optical energy gap (Tauc gap) calculated from absorption data is influenced by annealing temperatures and reactive process gas mixture. Changes in optical properties were correlated to the chemical modifications in the films due to annealing, through X-ray photoelectron spectroscopy. Studies reveal that the carbon and nitrogen concentrations in the films are highly sensitive to temperature. Annealing at higher temperatures leads to broken C–N bonds which results in the loss of C and N in the films. This is believed to be the primary cause for variations in optical properties of the films.     

Effect of solvent on structure and optical properties of PZT nanoparticles prepared by sol-gel method, in infrared region

Single-phase perovskite Pb(Zr_0.52,Ti_0.48) nanoparticles, PZT-NPs were prepared by the sol-gel method with two different solvents, 2-methoxyethanol, EGME, and poly ethylene glycol, PEG. X-ray diffraction (XRD) was used to study of the structure of the PZT-NPs. Fourier transform infrared spectroscopy (FTIR) was used to measure the infrared reflectivity spectrum in the range of 4000-280 cm⁻¹. Infrared active vibration modes of BO₆ octahedral (ν₁ and ν₂) were observed for PZT-NPs below 600 cm⁻¹. The third vibration mode of Pb against the TiO₃ group, ν₃, occurred below the experimentally accessible range. The Kramers-Kronig method (K-K) and classical dispersion theory were applied to analyze the data and calculation of the optical constants such as reflective index (N(ω))and permittivity (?(ω)). The results showed that the structure and optical properties of PZT-NPs were changed by different type of solvent.     

Effect of Al2O3 particle size on preparation and properties of ZTA ceramics formed by gelcasting

Zirconia-toughened alumina (ZTA) ceramics were prepared using three different kinds of Al₂O₃ powders (marked PW-A average particle size: 7.53 μm, marked PW-B average particle size: 1.76 μm, marked PW-C average particle size: 0.61 μm) by gelcasting. Effect of Al₂O₃ particle size on zeta potential, dispersant dosage and solid volume fractions of ZTA suspensions as well as the mechanical properties of ZTA green bodies and ceramics were investigated. The optimum dosages of dispersant for ZTA suspensions prepared by PW-A, PW-B and PW-C are 0.4 wt%, 0.5 wt% and 0.7 wt%, respectively. The highest solid volume fractions of ZTA suspensions can reach 62 vol% (SP-A), 60 vol% (SP-B) and 52 vol% (SP-C), respectively. The green bodies show a bending strength as high as 20 MPa, which can meet the requirement of machining. The Al₂O₃ powder with fine particle size is beneficial to the improvement of mechanical properties. The ZTA ceramics prepared by PW-B Al₂O₃ powder show the highest bending strength (680 MPa) and toughness (7.49 MPa m^1/2).     

Growth of 20 mol% Gd-doped ceria thin films by RF reactive sputtering: The O2/Ar flow ratio effect

The search for optimal materials and the utilization of proper manufacturing techniques to replace conventional electrolytes are our research objectives for the operation of solid oxide fuel cells under intermediate temperatures. Furthermore, understanding the effects of process parameters will be helpful for obtaining suitable materials for applications. In this study, we investigate the O₂/Ar flow ratio effect by employing RF reactive sputtering to fabricate 20 mol% Gd-doped ceria (20GDC) films on alumina substrates. The morphology of films was aggregated by nano-scale size of grains which gradually reduced in size from lower to higher O₂/Ar flow ratios. The microstructure of films was transferred from incomplete oxidized materials to well-crystallized cubic fluorite structures using an increased O₂/Ar flow ratio up to 0.30. The oxygen/metal ratio of films was increased gradually and saturated around 2.05 for O₂/Ar flow ratios over 0.25 and remained in uniform composition through whole films for each flow ratios.     

The role of zircon particle size distribution, surface area and contamination on the properties of silica-zircon ceramic materials

Zircon is used as an additive to silica ceramics for use in investment casting to improve their high temperature properties. However, little is known about the mechanisms by which this occurs. To investigate the effect of zircon addition to a silica ceramic a number of silica-zircon formulations were created utilising three different batches of zircon with different particle size distributions (PSDs), surface areas and contaminant inclusions. The contaminant inclusion of the zircon, present in the zircon from the ball-milling stage of manufacture, appeared to have a large effect on the room temperature flexural strength, high temperature flexural strength and high temperature creep properties. It is also suggested that any increase in post-fired cristobalite content and any change to crystal growth morphology was due to the inherent contaminant inclusions and not because of the zircon itself. Hence, use of silica-zircon materials in ceramics for investment casting should account for variation in the contaminant inclusion of the zircon in order to maintain the specific material properties required.     

Effect of Mn-doping on optical properties of lead-free (K0.4Na0.6)NbO3 ferroelectric single crystals

Optical properties of <001>-oriented pure (K_0.4Na_0.6)NbO₃ (KNN) and 0.5 wt% Mn-doped KNN (Mn-KNN) single crystals were studied. The refractive indices (n) of both crystals exhibited a normal dispersion behavior in the wavelength range of 300−1100 nm. The modified Sellmeier dispersion equations for n were obtained by least-squares fit. In addition, Sellmeier coefficients were determined by single-oscillator dispersion relation, which related to energy band structures of crystals. Compared with KNN, a decrease about 10 % in transmittance (over 350 nm) was observed in Mn-KNN due to the losses resulting from the increase of domain wall density. Furthermore, a 20 nm blue-shift in the absorption edge was observed for Mn-KNN. Based on Tauc equation, the band gap energies of 3.26 and 3.42 eV were obtained for KNN and Mn-KNN, respectively. The increase of band gap energy in Mn-KNN was attributed to the distortion of BO₆ octahedron building block caused by Mn²⁺ occupying the B-site.     

Synthesis and characterization of Fe doped titanium dioxide nanopowders

Titanium dioxide nanopowders, doped with different amounts of Fe³⁺ ions (0.3-5 mass%), were synthesized by acid-catalyzed sol-gel method in a non-aqueous medium. The obtained powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy and determination of izoelectric points as well as particle diameters. Careful investigation of porous structure was provided by application of nitrogen adsorption-desorption method. Structure analysis showed that the obtained nanopowders exhibited the anatase crystal structure, independent of the amount of iron dopants. The presence of Fe³⁺ ions in anatase decreases the value of isoelectric point of undoped TiO₂. Unlike crystal structure, porosity parameters are strongly affected by the amount of iron ions incorporated in TiO₂ lattice. The mesoporosity of TiO₂ can be successfully controlled by changing the amount of iron dopants.     

Effects of Ni doping on structural,optical and dielectric properties of ZnO

Structural, optical and dielectric properties of Ni doped ZnO samples prepared by the solid state route are presented. X-ray diffraction confirmed the substitution of Ni on Zn sites without changing the hexagonal structure of ZnO. NiO phase appeared for 6% Ni doping. Fourier transform infrared measurements were carried out to study phonon modes in Ni doped ZnO. Significant blueshift with Ni doping was observed in UV–visible studies, strongly supported by photoluminescence spectra that show a high intensity UV emission peak followed by the low intensity green emission band corresponding to oxygen vacancies and defects. The photoluminescence analysis suggest that doping of Ni can affect defects and oxygen vacancies in ZnO and give the possibility of band gap tuning for applications in optoelectronic devices. High values of dielectric constant at low frequency and a strong dielectric anomaly around 320 °C were observed.     

Effect of CeO2 addition on densification and microstructure of Al2O3-YSZ composites

Alumina (Al₂O₃) and alumina-yttria stabilized zirconia (YSZ) composites containing 3 and 5 mass% ceria (CeO₂) were prepared by spark plasma sintering (SPS) at temperatures of 1350-1400 °C for 300 s under a pressure of 40 MPa. Densification, microstructure and mechanical properties of the Al₂O₃ based composites were investigated. Fully dense composites with a relative density of approximately 99% were obtained. The grain growth of alumina was inhibited significantly by the addition of 10 vol% zirconia, and formation of elongated CeAl₁₁O₁₈ grains was observed in the ceria containing composites sintered at 1400 °C. Al₂O₃-YSZ composites without CeO₂ had higher hardness than monolithic Al₂O₃ sintered body and the hardness of Al₂O₃-YSZ composites decreased from 20.3 GPa to 18.5 GPa when the content of ZrO₂ increased from 10 to 30 vol%. The fracture toughness of Al₂O₃ increased from 2.8 MPa m^1/2 to 5.6 MPa m^1/2 with the addition of 10 vol% YSZ, and further addition resulted in higher fracture toughness values. The highest value of fracture toughness, 6.2 MPa m^1/2, was achieved with the addition of 30 vol% YSZ.     

Synthesis and dielectric properties of polyaniline/titanium dioxide nanocomposites

Two series of polyaniline–TiO₂ nanocomposite materials were prepared in base form by in situ polymerization of aniline with inorganic fillers using TiO₂ nanoparticles (P25) and TiO₂ colloids (Hombikat), respectively. The effect of particle sizes and contents of TiO₂ materials on their dielectric properties was evaluated. The as-synthesized polyaniline–TiO₂ nanocomposite materials were characterized by transmission electron microscopy (TEM), Fourier transform infrared (FTIR), thermal analysis (DTA/TGA), and X-ray diffraction (XRD). Dielectric properties of polyaniline–TiO₂ nanocomposites in the form of films were measured at 1 KHz–1 MHz and a temperature range of 35–150 °C. Higher dielectric constants and dielectric losses of polyaniline–TiO₂ nanocomposites than those of neat PANI were found. PANI–TiO₂ nanocomposites derived from P25 exhibited higher dielectric constants and losses than those from Hombikat TiO₂ colloids. Electrical conductivity measurements indicate that the conductivity of nanocomposites is increased with TiO₂ content. The dielectric properties and conductivities are considered to be enhanced due to the addition of TiO₂, which might induce the formation of a more efficient network for charge transport in the base polyaniline matrix.     

Evaluation of mechanically treated cerium (IV) oxides as corrosion inhibitors for galvanized steel

The use of cerium salts as corrosion inhibitors for hot dip galvanized steel has been object of a numerous studies in the last few years. The role of cerium ions as corrosion inhibitors was proved: cerium is able to block the cathodic sites of the metal, forming insoluble hydroxides and oxides on the zinc surface. This fact leads to a dramatic decrease of the cathodic current densities and, therefore, to a reduction the overall corrosion processes. On the other hand, the potential of cerium oxides as corrosion inhibitors was also proposed. However, the real effectiveness of this kind of anticorrosive pigments has not been clarified yet.In this work cerium (IV) oxides are considered as corrosion inhibitors for galvanized steel. The corrosion inhibition mechanism of mechanically treated (milled) CeO₂ alone and in combination with milled SiO₂ nanoparticles was investigated. For this purpose milled CeO₂, CeO₂ and SiO₂ milled together and milled SiO₂ particles were studied as corrosion inhibitors in water solution. Therefore, the different mechanically treated particles were dispersed in 0.1 M NaCl solution to test their effectiveness as corrosion inhibitors for galvanized steel. The galvanized steel was immersed in the different solutions and the corrosion inhibition efficiency of the different particles was measured by means of electrochemical techniques. For this purpose, electrochemical impedance spectroscopy (EIS) measurements were carried out, monitoring the evolution of the corrosion processes occurring at the metal surface with the immersion time in the solution. The effect of the different pigments was also investigated by carrying out anodic and cathodic polarization measurements. The polarization curves were acquired under conditions of varied pH. The experimental measurements suggest that the mechanical treatment performed on the SiO₂ and CeO₂ particles promote the formation of an effective corrosion pigment. The tests evidence also the beneficial effect of the CeO₂ milled particles when used in combination with the mechanically treated SiO₂ particles. It was proved that in alkaline conditions the effect of the mechanically treated CeO₂ and SiO₂ particles is dramatically increased.     

Porous ceramics with tri-modal pores prepared by foaming and starch consolidation

Porous silica ceramics with tri-modal pores were prepared, based on the generation of foams from silica/starch composite slurry and the subsequent stabilization of the structure by starch consolidation. The rheology of the original slurry and the foamed one were evaluated and compared. After drying, the green bodies were debindered and sintered at 1250 °C for 5 h. The resulting materials consisted of a hierarchical structure with large-sized cells, moderate-sized pores in cell wall and small-sized voids among silica grains. The compressive strength of the sintered samples varied within the range of 4–17 MPa, corresponding to relative densities of 18–30%.     

Camphor sulfonic acid doped polyaniline-tin oxide hybrid nanocomposites: Synthesis,structural, morphological,optical and electrical transport properties

Camphor sulfonic acid (CSA) doped PANi–SnO₂ hybrid nanocomposites were synthesized by solid-state synthesis route with varying amounts (10–50%) of CSA. X-ray diffraction studies have proven the successful incorporation of CSA into the polyaniline–SnO₂ hybrid nanocomposites and the results are also supported by microstructural analysis. UV–visible and Fourier infrared spectroscopy studies have provided insight into the electronic interaction between the CSA, polyaniline, and SnO₂. The room temperature dc electrical conductivity of CSA-doped PANi–SnO₂ hybrid nanocomposite films were observed to depend on the amount of CSA doping and the morphology.