Effect of Y2O3 and Er2O3 co-dopants on phase stabilization of bismuth oxide

Bi₂O₃ compositions were prepared to investigate the effect of rare earth metal oxides as co-dopants on phase stability of bismuth oxide. Compositions containing 9-14 mol% of Y₂O₃ and Er₂O₃ were synthesized by solid state reaction. The structural characterization was carried out using X-ray powder diffraction. The XRD results show that the samples containing 12 and 14 mol% total dopants had cubic structure, whereas the samples with lower dopant concentrations were tetragonal. Comparing the lattice parameters of the cubic phases of (Bi₂O₃)_0.88(Y₂O₃)_0.06(Er₂O₃)_0.06 and (Bi₂O₃)_0.86(Y₂O₃)_0.07(Er₂O₃)_0.07 revealed that lattice parameter decreases by increasing the dopant concentration. The XRD pattern and the powder density results indicated the formation of solid solution in the studied systems. After annealing samples with cubic phase at 600 °C for various periods of time, phase transformation to tetragonal and rhombohedral occurs.     

Laser stereolithography of ZrO2 toughened Al2O3

Ceramic laser stereolithography is a manufacturing process suitable candidate for the production of complex shape technical ceramics. The green ceramic is produced layer by layer through laser polymerisation of UV curable ceramic suspensions. A number of critical issues deserve attention: high solid loading and low viscosity of the suspensions, high UV reactivity, prevention of interlayer delamination in the green and in the sintered body, good mechanical performance. In this work, ZrO₂-reinforced Al₂O₃ components have been obtained from an acrylic modified zircon loaded with alumina powders. The zircon compound is effective as organic photoactivated resin and allows the dispersion of a high volume fraction of Al₂O₃ powder (up to 50 vol.%) while keeping viscosity at reasonable low values. The zircon compound also represents a liquid ceramic precursor that converts to oxide after burning out of the binder. Thank to the good dispersion of the alumina powder in the zircon acrylate, a uniform dispersion of ZrO₂ submicron particles is obtained after pyrolysis. These are located at the grain boundaries between alumina grains. Formation of both monoclinic and tetragonal ZrO₂ occurs as evidenced by XRD. No delamination occurs in bending tests as evidenced by SEM fractography, satisfactory modulus and strength values were concurrently found.     

Corrosion mechanisms of Al2O3/MgAl2O4 by V2O5, NiO, Fe2O3 and vanadium slag

The effects of V₂O₅, NiO, Fe₂O₃ and vanadium slag on the corrosion of Al₂O₃ and MgAl₂O₄ have been investigated. The specimens of Al₂O₃ and MgAl₂O₄ with the respective oxides above mentioned were heated at 10 °C/min from room temperature up to three different temperatures: 1400, 1450 and 1500 °C. The corrosion mechanisms of each system were followed by XRD and SEM analyses. The results obtained showed that Al₂O₃ was less affected by the studied oxides than MgAl₂O₄. Alumina was only attacked by NiO forming NiAl₂O₄ spinel, while the MgAl₂O₄ spinel was attacked by V₂O₅ forming MgV₂O₆. It was also observed that Fe₂O₃ and Mg, Ni, V and Fe present in the vanadium slag diffused into Al₂O₃. On the other hand, the Fe₂O₃ and Ca, S, Si, Na, Mg, V and Fe diffused into the MgAl₂O₄ structure. Finally, the results obtained were compared with those predicted by the FactSage software.     

The catalytic performance in oxidative coupling of methane and the surface basicity of La2O3, Nd2O3, ZrO2 and Nb2O5

The catalytic performance in oxidative coupling of methane (OCM) of unmodified pure La₂O₃, Nd₂O₃, ZrO₂ and Nb₂O₅ has been investigated under various conditions. The results confirmed that the activity of La₂O₃ and Nd₂O₃ was always much higher than that of the remaining two. The surface basicity/base strength distribution of pure La₂O₃, Nd₂O₃, ZrO₂ and Nb₂O₅ was measured using a test reaction of transformation of 2-butanol and a temperature-programmed desorption of CO₂. Both methods showed that La₂O₃ and Nd₂O₃ had high basicity and contained medium and strong basic sites (lanthanum oxide more and neodymium oxide somewhat less). ZrO₂ had only negligible amount of weak basic sites and Nb₂O₅ was rather acidic. The confrontation of the basicity and catalytic performance indicated that in the case of investigated oxides, the basicity (especially strong basic sites) could be a decisive factor in determination of the catalytic activity in OCM. Only in the case of ZrO₂ it was observed a moderate catalytic performance in spite of negligible basicity. The influence of a gas atmosphere used in the calcination of oxides (flowing oxygen, helium and nitrogen) on their basicity and catalytic activity in OCM had been also investigated. Contrary to earlier observations with MgO, no effect of calcination atmosphere on the catalytic performance of investigated oxides in OCM and on their basicity was observed.     

Dynamic corrosion of Al2O3-ZrO2-SiO2 and Cr2O3-containing refractories by molten frits. Part II: Microstructural study

In this work results on dynamic corrosion studies of fused cast Al₂O₃-SiO₂-ZrO₂ and isostatically pressed and sintered Cr₂O₃-based refractories by two crystalline (transparent) frits are described. Experiments have been performed using the “Merry Go Round” test at ≅1500 °C.Microstructural and mineralogical analyses of selected areas from the corroded regions of the studied refractories were performed by reflected light optical microscopy and scanning electron microscopy with analysis by X-ray dispersive energy.Significant differences between the corrosion mechanisms acting in the two types of materials were found. In the fused cast Al₂O₃-SiO₂-ZrO₂ specimens corrosion took place by the dissolution of alumina and zirconia in the frit and in the glass formed by the reaction between the frit and the refractory. In the Cr₂O₃-based materials the corrosion process was controlled by the capillar penetration of the molten frit through the open pores. The reaction between the ZnO from the frits and Cr₂O₃ led to the formation of spinel (ZnCr₂O₄), a high-melting point bonding phase that retarded the frit penetration. Results are discussed using the relevant phase equilibrium diagrams.     

Long-term degradation of Ta2O5-doped Bi2O3 systems

Bismuth oxide in δ-phase is a well-known high oxygen ion conductor and can be used as an electrolyte for intermediate temperature solid oxide fuel cells (IT-SOFCs). 5-10 mol% Ta₂O₅ are doped into Bi₂O₃ to stabilize δ-phase by solid state reaction process. One Bi₂O₃ sample (7.5TSB) was stabilized by 7.5 mol% Ta₂O₅ and exhibited single phase δ-Bi₂O₃-like (type I) phase. Thermo-mechanical analyzer (TMA), X-ray diffractometry (XRD), AC impedance and high-resolution transmission electron microscopy (HRTEM) were used to characterize the properties. The results showed that holding at 800-850 °C for 1 h was the appropriate sintering conditions to get dense samples. Obvious conductivity degradation phenomenon was obtained by 1000 h long-term treatment at 650 °C due to the formation of α-Bi₂O₃ phase and Bi₃TaO₇, and 〈1 1 1〉 vacancy ordering in Bi₃TaO₇ structure.     

Synthesis of LiNi0.9Co0.1O2 from Li2CO3, NiO or NiCO3, and CoCO3 or Co3O4 and their electrochemical properties

Cathode active materials with a composition of LiNi_0.9Co_0.1O₂ were synthesized by a solid-state reaction method at 850 °C using Li₂CO₃, NiO or NiCO₃, and CoCO₃ or Co₃O₄, as the sources of Li, Ni, and Co, respectively. Electrochemical properties, structure, and microstructure of the synthesized LiNi_0.9Co_0.1O₂ samples were analyzed. The curves of voltage vs. x in Li_xNi_0.9Co_0.1O₂ for the first charge–discharge and the intercalated and deintercalated Li quantity Δx were studied. The destruction of unstable 3b sites and phase transitions were discussed from the first and second charge–discharge curves of voltage vs. x in Li_xNi_0.9Co_0.1O₂. The LiNi_0.9Co_0.1O₂ sample synthesized from Li₂CO₃, NiO, and Co₃O₄ had the largest first discharge capacity (151 mA h/g), with a discharge capacity deterioration rate of −0.8 mA h/g/cycle (that is, a discharge capacity increasing 0.8 mA h/g per cycle).     

Sintering of Al2O3-SiC composite from sol-gel method with MgO, TiO2 and Y2O3 addition

Al₂O₃-SiC composite ceramics were prepared by pressureless sintering with and without the addition of MgO, TiO₂ and Y₂O₃ as sintering aids. The effects of these compositional variables on final density and hardness were investigated. In the present article at first α-Al₂O₃ and β-SiC nano powders have been synthesized by sol-gel method separately by using AlCl₃, TEOS and saccharose as precursors. Pressureless sintering was carried out in nitrogen atmosphere at 1600 °C and 1630 °C. The addition of 5 vol.% SiC to Al₂O₃ hindered densification. In contrast, the addition of nano MgO and nano TiO₂ to Al₂O₃-5 vol.% SiC composites improved densification but Y₂O₃ did not have positive effect on sintering. Maximum density (97%) was achieved at 1630 °C. Vickers hardness was 17.7 GPa after sintering at 1630 °C. SEM revealed that the SiC particles were well distributed throughout the composite microstructures. The precursors and the resultant powders were characterized by XRD, STA and SEM.     

Phase diagram of the Al2O3-HfO2-Y2O3 system

The phase diagram of the Al₂O₃-HfO₂-Y₂O₃ system was first constructed in the temperature range 1200-2800 °C. The phase transformations in the system are completed in eutectic reactions. No ternary compounds or regions of appreciable solid solution were found in the components or binaries in this system. Four new ternary and three new quasibinary eutectics were found. The minimum melting temperature is 1755 °C and it corresponds to the ternary eutectic Al₂O₃ + HfO₂ + Y₃Al₅O₁₂. The solidus surface projection, the schematic of the alloy crystallization path and the vertical sections present the complete phase diagram of the Al₂O₃-HfO₂-Y₂O₃ system.     

Synthesis and optical characterization of novel Sr3Ga2O6:Eu phosphor

Alkaline earth metal gallets have been identified as an important ceramic material. The crystal chemistry of many of these gallets is well explored; however, very rare studies regarding optical properties of rare earth (RE) ions doped in such gallets, particularly in Sr₃Ga₂O₆ host, have been carried out. The present study reports on synthesis and characterization of novel Sr₃Ga₂O₆:Eu³⁺ phosphors. The phosphors have been synthesized using a conventional solid state reaction method. Crystal structure, morphology and luminescence properties (excitation, emission and CIE coordinate) of these phosphors have been studied as a function of sintering temperature and Eu³⁺ concentration. X-ray diffraction study reveals that the phosphor sintered at low temperature (900 °C) contains an impurity phase which is removed at higher sintering temperatures and results into cubic crystalline phase of Sr₃Ga₂O₆. Particle size of the phosphor increases with an increase in sintering temperature which results to a red shift in the peak position of excitation band lying in a broad range from 250 to 370 nm. Optimum emission intensity is attained for 0.12 mol% concentration of Eu³⁺ ions; above this concentration, a quenching in emission intensity is observed.     

Phase stability and electric conductivity of Er2O3-Nb2O5 co-doped Bi2O3 electrolyte

Two oxides, Er₂O₃ and Nb₂O₃, are used to stabilize delta-phase Bi₂O₃ used as electrolyte of solid oxide fuel cell. Optimization of dopant ratio and total doping concentration (TDC) is determined by X-ray diffraction, and successfully reduce the TDC (Er + Nb) to 10-15 mol.%. Conductivities of different compositions are measured by two-probe method. The results show that highest conductivity appears at the minimum doping concentrations. Phase stability of ENSB samples with Er/Nb ratio of 2/1 and TDC of 10-20 mol.% at 650 °C up to 300 h is analyzed showing two newly formed (alpha- and gamma-) phases in the samples. Degradation of conductivity at 650 °C is studied in detail by DTA and TEM. The abnormity of lattice contraction of delta-phase is discussed.     

Development of input output relationships for self-healing Al2O3/SiC ceramic composites with Y2O3 additive using design of experiments

Al₂O₃/SiC ceramic composites with Y₂O₃ as an additive, was synthesized using the Taguchi method of design of experiments, so as to develop statistically sound input output relationships. The proportion of SiC was varied from 12 to 21 vol.% whereas that of Y₂O₃ was varied from 2.5 to 4 vol.%. The composites were sintered at 1500 °C for a soaking time period of 12 h in an air atmosphere. Cracks were induced on the composite surface using a Vickers indenter with a load varying between 20 and 40 kg. Fractographical analyses have been carried out using optical and/or scanning electron microscopy to investigate the surface crack propagation behavior. Thermal aging at 1300 °C in the time range of 0.5-12.5 h was applied to find optimal conditions for healing of the pre-cracked samples. The output parameters such as crack length, healed crack length, hardness and fracture toughness of the samples were correlated with appropriate inputs such as contents of SiC and Y₂O₃, crack-healing temperature, healing time, compaction pressure, indentation load using statistical analysis. Further, the extent of influence, exerted by pertinent input parameters on output parameters, was also identified.     

Improvement of coke resistance of Ni/Al2O3 catalyst in CH4/CO2 reforming by ZrO2 addition

This work investigates the improvement of Ni/Al₂O₃ catalyst stability by ZrO₂ addition for H₂ gas production from CH₄/CO₂ reforming reactions. The initial effect of Ni addition was followed by the effect of increasing operating temperature to 500–700 °C as well as the effect of ZrO₂ loading and the promoted catalyst preparation methods by using a feed gas mixture at a CH₄:CO₂ ratio of 1:1.25. The experimental results showed that a high reaction temperature of 700 °C was favored by an endothermic dry reforming reaction. In this reaction the deactivation of Ni/Al₂O₃ was mainly due to coke deposition. This deactivation was evidently inhibited by ZrO₂, as it enhances dissociation of CO₂ forming oxygen intermediates near the contact between ZrO₂ and nickel where the deposited coke is gasified afterwards. The texture of the catalyst or BET surface area was affected by the catalyst preparation method. The change of the catalyst texture resulted from the formation of ZrO₂–Al₂O₃ composite and the plugging of Al₂O₃ pore by ZrO₂. The 15% Ni/10% ZrO₂/Al₂O₃ co-impregnated catalyst showed a higher BET surface area and catalytic activity than the sequentially impregnated catalyst whereas coke inhibition capability of the promoted catalysts prepared by either method was comparable. Further study on long-term catalyst stability should be made.     

Mechanism and kinetics of Al2O3 nanoparticles formation by reaction of bulk Al with H2O and CO2 at sub- and supercritical conditions

Oxidation of bulk samples of 〈Al〉 by water and H₂O/CO₂ mixture at sub- and supercritical conditions for uniform temperature increase and at the injection of H₂O (665 K, 23.1 MPa) and H₂O/CO₂ (723 K, 38.0 MPa) fluids into the reactor has been studied. Transition of 〈Al〉 into AlOOH and Al₂O₃ nanoparticles has been found out. Aluminum samples oxidized by H₂O and H₂O/CO₂ fluids at the injection mostly consist of large particles (300-500 nm) of α-Al₂O₃. Those oxidized for uniform temperature increase contain smaller particles (20-70 nm) of γ-Al₂O₃ as well. Mechanism of this phenomenon is explained by orientation of oxygen in H₂O polar molecules to the metal in the electric field of contact voltage at Al/AlOOH and Al/Al₂O₃ boundary. Addition of CO₂ to water resulted in CO, CH₄, CH₃OH and condensed carbon, increase in size of Al₂O₃ nanoparticles and significant decrease in time delay. In pure CO₂ 〈Al〉 oxidation resulted in oxide film. Using temperature and time dependences of gaseous reactant pressure and Redlich-Kwong state equation, kinetics of H₂ formation has been described and oxidation regularities determined. At aluminum oxidation by H₂O and H₂O/CO₂ fluids, self-heating of the samples followed by oxidation rate increase has been registered. The samples of oxidized aluminum have been studied with a transmission electronic microscope, a thermal analyzer and a device for specific surface measurement. The effect of oxidation conditions on the characteristics of synthesized nanoparticles has been found out.     

Densification ability of combustion-derived Al2O3 powders

Nanocrystalline Al₂O₃ powders containing different amounts of MgO (0.1–5.0 mol%) or added boehmite (AlOOH) have been synthesized by combustion synthesis from aluminium nitrate and magnesium nitrate, using urea or sucrose as fuels. The as synthesized alumina powders were deagglomerated, compacted by dry pressing and sintered at 1625 °C for 2 h. For comparison purposes, a commercial high purity α-Al₂O₃ powder (ACC) was also processed following the same route. The sintered materials were characterized for bulk density (BD), apparent porosity (AP), and water absorption (WA) capacity, microstructure using SEM, and XRD phase composition. In comparison to boehmite, the MgO had a considerable effect on the densification behaviour of combustion-synthesized powder.     

Dynamic corrosion of Al2O3-ZrO2-SiO2 and Cr2O3-containing refractories by molten frits. Part I: Macroscopic analysis

Manufacturing of enamels and frits has undergone dramatic changes since the 1980s. This has required significant efforts in research and development. Typical compositions of frits for ceramic tiles are silica-based with fluxing agents; some of the components are highly corrosive. Improvements in the production of frits would imply the selection of the most adequate refractories as a function of the chemical composition of the considered frit and the fabrication procedure.The refractories currently used in frit furnaces are Al₂O₃-ZrO₂-SiO₂ (AZS) fused cast materials and Cr₂O₃-based materials. In this work, results on dynamic corrosion studies of AZS and Cr₂O₃-based materials by two ZnO-containing frits are described. Experiments have been performed using the “Merry Go Round” test at ≅1500 °C. Macroscopic results are analysed in terms of the remaining volume after the tests, as usually done in the glass industry. The significance and limits of such an approach are discussed.     

SO2 and NO removal from flue gas over V2O5/AC at lower temperatures — role of V2O5 on SO2 removal

Supporting V₂O₅ onto an activated coke (AC) has been reported to significantly increase the AC's activity in simultaneous SO₂ and NO removal from flue gas. To understand the role of V₂O₅ on SO₂ removal, V₂O₅/AC is studied through SO₂ removal reaction, surface analysis, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) techniques. It is found that the main role of V₂O₅ in SO₂ removal over V₂O₅/AC is to catalyze SO₂ oxidation through a VOSO₄-like intermediate species, which reacts with O₂ to form SO₃ and V₂O₅. The SO₃ formed transfers from the V sites to AC sites and then reacts with H₂O to form H₂SO₄. At low V₂O₅ loadings, a V atom is able to catalyze as many as 8 SO₂ molecules to SO₃. At high V₂O₅ loadings, however, the number of SO₂ molecules catalyzed by a V atom is much less, due possibly to excessive amounts of V₂O₅ sites in comparison to the pores available for SO₃ and H₂SO₄ storage.     

Matrix–filler interactions in polysilazane-derived ceramics with Al2O3 and ZrO2 fillers

Interactions between a poly(vinyl)silazane and Al₂O₃ or Y₂O₃-stabilised ZrO₂ fillers were studied during the fabrication of polysilazane-derived bulk ceramics in order to investigate the influence of oxide fillers on resulting properties. Specimens were produced by coating of the filler powders with the polysilazane, warm-pressing of the resulting composite powders, and pyrolytic conversion in flowing N₂ at various temperatures between 1000 °C and 1400 °C. Significant differences in densification were observed, depending on the filler used. Reactions between the polysilazane-derived matrix and Al₂O₃ or ZrO₂ at temperatures ≥1300 °C resulted in the formation of Si₅AlON₇ or ZrSiO₄, respectively. Reactivity in the polysilazane-derived component was a result of SiO₂ contamination caused primarily by adsorbed species on the filler particle surface. Knowledge of polysilazane/filler interface processes is found to be decisive for the prediction of properties such as shrinkage and porosity, which heavily influence performance of a material.     

Indirect selective laser sintering of epoxy resin-Al2O3 ceramic powders combined with cold isostatic pressing

To fabricate Al₂O₃ ceramic components with complex shape, selective laser sintering (SLS) combined with cold isostatic pressing (CIP) process was used to consolidate Al₂O₃ powder with additive of epoxy resin E06 (ER06) and polyvinyl alcohol (PVA). The starting material preparation combined spray drying with mechanical mixing to formulate compound powder consisting of PVA (1.5 wt%), ER06 (8 wt%) and Al₂O₃ and provide a good fluidity for SLS. Experimental investigations were carried the shrinkage, relative density, bending strength of Al₂O₃-ER06 SLS specimens in order to optimize the laser sintering parameters. It was found that Al₂O₃-ER06 SLS specimens represented acceptable shrinkage, high density and bending strength when laser power, scanning speed, scanning space and layer thickness were, respectively, 21 W, 1600 mm/s, 100 μm and 150 μm. Following that, the SLS specimens were processed through CIP to eliminate the pores in green ceramics. Finally, the optimized SLS/CIP Al₂O₃ specimens were debinded, sintered to produce crack-free Al₂O₃ bodies. The final Al₂O₃ components achieved a relative high density of more than 92% after furnace sintering. The study shows a novel and promising approach to fabricate complex ceramic matrix and ceramic components via indirect SLS and CIP process.