Aqueous tape casting and crystallization behavior of gadolinium-doped ceria

An aqueous tape casting of gadolinia-doped ceria (GDC) ceramics was developed using Poly(acrylic acid) PAA as dispersant, Poly(vinyl alcohol) PVA as binder, Poly(ethylene glycol) PEG as plasticizer, and deionized water as solvent. Surface properties of GDC powder with and without PAA dispersant were characterized by electrokinetic measurements. The zeta potential measurement revealed that the isoelectric point for GDC powders in the absence of dispersant corresponds to a pH value of 4.06. The experimental results showed that pH value greatly affects the rheology of the slurry. Homogeneous, smooth, and defect-free green tapes were successfully obtained by using an appropriate slurry formula. Moreover, the crystallization kinetics of GDC powders prepared by coprecipitation process also has been investigated in this study. The activation energy of crystallization was calculated by differential scanning calorimetry (DSC) at different heating rates. Analysis of non-isothermal DSC data presented values of 105.3 kJ/mol and 1.171 for the activation energy of crystallization presented and the Avrami exponent, respectively.     

Copper oxide catalysts supported on ceria for low-temperature CO oxidation

Copper oxide catalysts supported on ceria were prepared by wet impregnation method using finely CeO₂ nanocrystals, which was derived from alcohothermal synthesis, and copper nitrate dissolved in the distilled water. The catalytic activity of the prepared CeO₂ and CuO/CeO₂ catalysts for low-temperature CO oxidation was investigated by means of a microreactor-GC system. The samples were characterized using BET, XRD, SEM, HRTEM and TPR.     

Tape casting of UV-curable aluminium nitride-based slurries

Aluminium nitride (AlN) is one of the materials used for the preparation of substrates for electronic circuits. Such substrates can be prepared via tape casting method. Until now, only non-aqueous and aqueous tape casting was developed and studied for AlN. In this work, the development of UV-curable tape casting for AlN, including the use of photopolymerisable binder, is shown. Two different dispersing agents, BYK-W 9010 and glycerol trioleate, were used to stabilize and homogenize AlN dispersions. In order to modify the powder surface, a pre-treatment step was used, where the powder was first mixed with the dispersing agent in an azeotropic solvent mixture, followed by the evaporation of the solvents and the redispersing of the pre-conditioned powder into the reactive binder. The effective concentration of the dispersants, the impact of the solid loading on the viscosity and slurry behaviour, as well as the effect of the powder pre-conditioning, were studied by means of rheological measurements. Green tapes were optimised by evaluating the effect of the casting gap and the photo- and co-initiator concentrations. Finally, FTIR measurements were used to estimate the polymer conversion degree as a function of exposure time for the green tapes.     

Synthesis and characterization of Cu-doped ceria nanopowders

Nanopowdered solid solution Ce_1−xCu_xO_2−γ samples (0 ≤ x ≤ 0.15) were synthesized by self-propagating room temperature synthesis (SPRT). Raman spectroscopy and XRD at room temperature were used to study the vibration properties of these materials as well as the Cu solubility in ceria lattice. The solubility limit of Cu²⁺ in CeO₂ lattice was found to be lower than published in the literature. Results show that obtained powders with low dopant concentration are solid solutions with a fluorite-type crystal structure. However, with Cu content higher than 7.5 mass%, the phase separation was observed and two oxide phases, CeO₂ and CuO, coexist. All powders were nanometric in size with high specific surface area.     

Ceramic domes fabricated by a combination of tape casting and vacuum forming

Tape casting is a low cost fabrication process for flat ceramic sheet and this paper demonstrates how it can be combined with vacuum forming to make α-alumina domes of 250-300 μm sintered thickness. The suspension formulation makes use of systems of double plasticizers and double solvents in a poly(methyl methacrylate) binder to provide plastic ceramic films by tape casting from which preforms for vacuum forming were cut. In order to retain the shape of vacuum formed domes during debinding and sintering, an initial low temperature anneal is needed. The study indicates that the ratio of plasticizers to binder and the particle size are two dominant parameters in influencing the elongational flow. The whole process provides a novel method to make thin ceramic domes.     

Processing and performance of solid oxide fuel cell with Gd-doped ceria electrolyte

Fuel Cell performance was measured at 792-1095 K for Ni-GDC (Gd-doped ceria) anode-supported GDC film (60 μm thickness) with a (La_0.8Sr_0.2)(Co_0.8Fe_0.2)O₃ cathode using H₂ fuel containing 3 vol% H₂O. A maximum power density, 436 mW/cm², was obtained at 1095 K. The electrical conductivity of GDC electrolyte in N₂ atmosphere of 10⁻¹⁵-10⁰ Pa oxygen partial pressures (Po₂) at 773-1073 K was independent of Po₂, which indicated the diffusion of oxide ions. The conductivity of GDC in H₂O/H₂ atmosphere increased because of the further formation of electrons due to the dissociation of hydrogen in GDC (H₂ → 2H⁺ + 2e⁻). The hole conductivity was observed at 873 K in Po₂ = 10⁰-10⁴ Pa. The key factors in increasing power density are the increase of open circuit voltage and the suppression of H₂ fuel dissolution in GDC electrolyte. These are controlled by the cathode material and Gd-dopant composition.     

Quantification of microstructural features in gadolinia-doped ceria containing co-additives by digital image analysis

A digital image processing and analysis method has been developed to evaluate the microstructural features of chemically synthesized gadolinia-doped ceria powders containing small amounts of co-dopants. The effects of particles/clusters size, porosity and grain size distribution were examined in detail and compared to those parameters of the standard composition without co-dopants. In addition, the effect of the co-dopants in the grain growth was clarified. Sr²⁺ and Bi³⁺ act as sintering aid for densification of the standard composition. The lowest mean grain size along with higher fraction of porosity was obtained for Na⁺ addition.     

Analytical characterization of silane films modified with cerium activated nanoparticles and its relation with the corrosion protection of galvanised steel substrates

Galvanised steel substrates were pre-treated in bis-1,2-[triethoxysilyilpropyl]tetrasulphide silane solutions containing SiO₂ or CeO₂ nanoparticles activated with cerium ions. The surface composition was investigated by infrared spectroscopy. The film thickness was determined by scanning electron microscopy. The results showed that the barrier properties of silane films modified with nanoparticles depend upon the concentration of nanoparticles. The results also showed that the silane film thickness increases when the nanoparticles are activated with cerium ions. The anti-corrosion behaviour of the cerium activated nanoparticles was also investigated at the microscale level, in artificial induced defects, using the scanning vibrating electrode technique (SVET). The substrates treated with the silane coating modified with CeO₂ nanoparticles revealed improved corrosion behaviour comparatively to the coatings modified with SiO₂ nanoparticles. X-ray photoelectron spectroscopy and Auger electron spectroscopy experiments carried out on the defects after immersion in NaCl solutions revealed the presence of a surface film containing zinc corrosion products and cerium/ceria compounds.     

Cerium salt activated nanoparticles as fillers for silane films: Evaluation of the corrosion inhibition performance on galvanised steel substrates

The present work investigates the electrochemical behaviour of galvanised steel substrates pre-treated with bis-[triethoxysilylpropyl] tetrasulfide silane (BTESPT) solutions modified with SiO₂ or CeO₂ nanoparticles activated with cerium ions. The electrochemical behaviour of the pre-treated substrates was evaluated via electrochemical impedance spectroscopy in order to assess the role of the nanoparticles in the silane film resistance and capacitance. The ability of the Ce-activated nanoparticles to mitigate corrosion activity at the microscale level in artificial induced defects was studied via scanning vibrating electrode technique (SVET). Complementary studies were performed using potentiodynamic polarisation. The results show that the presence of nanoparticles reinforces the barrier properties of the silane films and that a synergy seems to be created between the activated nanoparticles and the cerium ions, reducing the corrosion activity. The addition of CeO₂ nanoparticles was more effective than the addition of SiO₂ nanoparticles.     

Modified solution combustion route for the preparation of plasma sprayable ceria powder

Plasma sprayable grade ceria powder was prepared by the solution combustion method. This is the first report on the application of solution combustion for the synthesis of plasma sprayable grade oxide powders. The fuels and fuel ratios used in the solution combustion were modified to achieve adequate flowability. It was found that when a mixture of fuels like glycine and ammonium acetate was used, the combustion process yielded larger agglomerates. Phase purity of the powders was confirmed by powder XRD. The morphology of the particles was determined by scanning electron microscopy.     

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.     

Tape casting of alumina/zirconia suspensions containing graphene oxide

The introduction of carbon derivatives (nanotubes, graphene, etc.) as a second phase in ceramic matrices has limitations arising from their difficult processing. This paper studies the colloidal stability and the rheological behaviour of concentrated suspensions of alumina with 5 vol.% Y-TZP (AZ) and the effect of the addition of 2 vol.% of graphene oxide (AZGO) on the suspension stability, rheological behaviour and tape casting performance. The colloidal stability was studied using zeta potential measurements in terms of concentration of deflocculants and pH and homogenisation was optimised adjusting the sonication mode and time. The best results were obtained for pulsed mode. The optimum rheological properties were obtained for solid loadings of 53 vol.% and 40 vol.% for AZ and AZGO. Homogeneous, flexible tapes with thickness of ∼120 μm were obtained reaching densities of >60% of theoretical density in which secondary phases are well dispersed.     

Influence of erbia or europia doping on crystal structure and microstructure of ceria–zirconia (CZ) solid solutions

In this study we have prepared three zirconia–ceria compositions, namely 12, 50 and 80 mole% CeO₂. Along with each pure ceria–zirconia composition we have prepared two parallel erbia- or europia-doped materials in which 0.5 mole% of each of the two starting oxides is replaced by 1 mole erbia or europia.     

Direct coagulation casting of YSZ powder suspensions using MgO as coagulating agent

Direct coagulation casting (DCC) of aqueous 8 wt% yttria stabilized zirconia (YSZ) powder suspensions prepared using ammonium poly(acrylate) dispersant has been studied using MgO as coagulating agent. Small amount (<0.1 wt% based on YSZ) of MgO powder dispersed in the YSZ powder suspension at ∼5 °C set the suspension in to stiff wet-coagulated body when exposed to room temperature (30 °C) due to the reaction between ammonium poly(acrylate) and MgO. MgO concentration equivalent to react with dispersant did not coagulate the YSZ powder suspension though it precipitate the whole ammonium poly(acrylate) dispersant as Mg-poly(acrylate). This is because of the ability of the YSZ powder to disperse in water at alkaline pH (∼9.5) without any dispersant by electrostatic mechanism. The YSZ powder suspensions form stiff coagulated bodies at MgO concentration double or more of the equivalent amount required for reacting with the dispersant. Setting of the YSZ powder suspension is due to the heterocoagulation of the YSZ particles and MgO particles added in excess of the equivalent amount to react with the dispersant, having opposite surface charges. The wet-coagulated body showed relatively high compressive yield strength (155 kPa) and Young’s modulus (3.1 MPa). The green bodies prepared by humidity controlled drying of the wet-coagulated bodies sintered to >98% TD at 1550 °C.     

Preparation and characterization of CeO2/TiO2 nanoparticles by flame spray pyrolysis

Nanocrystalline TiO₂, CeO₂ and CeO₂-doped TiO₂ have been successfully prepared by one-step flame spray pyrolysis (FSP). Resulting powders were characterized with X-ray diffraction (XRD), N₂-physisorption, Transmission Electron Microscopy (TEM) and UV-Vis spectrophotometry. The TiO₂ and CeO₂-doped TiO₂ nanopowders were composed of single-crystalline spherical particles with as-prepared primary particle size of 10-13 nm for Ce doping concentrations of 5-50 at%, while square-shape particles with average size around 9 nm were only observed from flame-made CeO₂. The adsorption edge of resulting powder was shifted from 388 to 467 nm as the Ce content increased from 0 to 30 at% and there was an optimal Ce content in association with the maximum absorbance. This effect is due to the insertion of Ce^3+/4+ in the TiO₂ matrix, which generated an n-type impurity band.     

Chemical reduction of nanocrystalline CeO2

The reduction of commercial and mechanochemically processed CeO₂ powders was studied. Nanostructured CeO₂, with the crystallite size of 21 nm and the lattice distortion of 0.37%, was obtained during 60 min of milling in a high-energetic vibratory mill. X-ray diffraction, scanning electron microscopy and Brunauer-Emmett-Teller method were applied to characterize the milled powders. During the thermal treatment at 1200 and 1400 °C in an argon atmosphere the nonstoichiometric CeO_2−x oxides with the defect fluorite structure were formed. Compositions of CeO_2−x oxides were determined according to its lattice parameter. The results showed that the release of oxygen, as well as the rate of reduction, was more effective in nanocrystalline then in the microcrystalline CeO₂, producing at 1200 °C CeO_1.80 and CeO_1.85 oxides, while at 1400 °C were obtained similarly, CeO_1.77 and CeO_1.78, compositions.     

Hydrogen production by oxidative steam reforming of methanol using ceria promoted copper–alumina catalysts

The performance of different Cu/CeO₂/Al₂O₃ catalysts of varying compositions is investigated for the oxidative steam reforming of methanol (OSRM) in order to produce the hydrogen selectively for polymer electrolyte membrane (PEM) fuel cell applications. All the catalysts were prepared by co-precipitation method and characterized for their surface area, pore volume and oxidation–reduction behavior. The effect of various operating parameters studied are as follows: reaction temperature (200–300 °C), contact-time (W/F = 3–15 kg_cat s mol^− 1) and oxygen to methanol (O/M) molar ratio (0–0.5). The steam to methanol (S/M) molar ratio = 1.5 and pressure = 1 atm were kept constant. Among all the catalysts studied, catalyst Cu–Ce–Al:30–20–50 exhibited 100% methanol conversion and 179 mmol s^− 1 kg_cat^− 1 hydrogen production rate at 280 °C with carbon monoxide formation as low as 0.19%. The high catalytic activity and hydrogen selectivity shown by ceria promoted Cu/Al₂O₃ catalysts is attributed to the improved specific surface area, dispersion and reducibility of copper which were confirmed by characterizing the catalysts through temperature programmed reduction (TPR), CO chemisorption, X-ray diffraction (XRD) and N₂ adsorption–desorption studies. Reaction parameters were optimized in order to produce hydrogen with carbon monoxide formation as low as possible. The time-on-stream stability test showed that the Cu/CeO₂/Al₂O₃ catalysts were quite stable.     

Synergistic effect of CeO2 modified Pt/C catalysts on the alcohols oxidation

The effect of the addition of CeO₂ to Pt/C catalysts on electrochemical oxidation of alcohols (methanol, ethanol, glycerol, ethylene glycol) was studied in alkaline solution. The ratios of Pt to CeO₂ in the catalysts were optimised to give the better performance. The electrochemical measurements revealed that the addition of CeO₂ into Pt-CeO₂/C catalysts could significantly improve the electrode performance for alcohols oxidation, in terms of the reaction activity and the poisoning resistance, due to the synergistic effect. The electrode with the weight ratio of Pt to CeO₂ equals 1.3:1 with platinum loading of 0.30 mg/cm² showed the highest catalytic activity for oxidation of ethanol, glycerol and ethylene glycol.     

High temperature desulfurization over nano-scale high surface area ceria for application in SOFC

In the present work, suitable absorbent material for high temperature desulfurization was investigated in order to apply internally in solid oxide fuel cells (SOFC). It was found that nano-scale high surface area CeO₂ has useful desulfurization activity and enables efficient removal of H2S from feed gas between 500 to 850°C. In this range of temperature, compared to the conventional low surface area CeO₂, 80–85% of H2S was removed by nano-scale high surface area CeO₂, whereas only 30–32% of H2S was removed by conventional low surface area CeO₂. According to the XRD studies, the product formed after desulfurization over nano-scale high surface area CeO₂ was Ce₂O₂S. EDS mapping also suggested the uniform distribution of sulfur on the surface of CeO₂. Regeneration experiments were then conducted by temperature programmed oxidation (TPO) experiment. Ce₂O₂S can be recovered to CeO₂ after exposure in the oxidation condition at temperature above 600°C. It should be noted that SO₂ is the product from this regeneration process. According to the SEM/EDS and XRD measurements, all Ce₂O₂S forming is converted to CeO₂ after oxidative regeneration. As the final step, a deactivation model considering the concentration and temperature dependencies on the desulfurization activity of CeO₂ was applied and the experimental results were fitted in this model for later application in the SOFC model.