Gelcasting of dense and porous ceramics by using a natural gelatine

An improved gel-casting procedure was successfully exploited to produce porous ceramic bodies having controlled porosity features in terms of mean pore size, total pore volume as well as pore geometry. The gel-casting process in which a natural gelatine for food industry is used as gelling agent was firstly set-up to prepare dense alumina and zirconia components. Then, commercial PE spheres, sieved to select proper dimensional ranges, were added to the starting slurries as pore-forming agent. Both alumina and zirconia porous bodies were then produced, having a porosity ranging between 40 and 50 vol%. The fired components were characterised by spherical pores surrounded by highly dense ceramic walls and struts, having a homogeneous and fine microstructure. Their mean pore size was directly dependent on the sieved fraction of the starting PE spheres selected as pore-forming phase.     

Preparation of calcium hexaluminate porous ceramics by gel-casting method with polymethyl methacrylate as pore-forming agent

Calcium hexaluminate (CA₆) porous ceramics were prepared by gel-casting method, with α-Al₂O₃ and CaCO₃ as raw materials and polymethyl methacrylate (PMMA) microspheres as pore-forming agent. The effects of the amount of pore-forming agent PMMA microspheres on the phase composition, bulk density, apparent porosity, flexural strength, microstructure, thermal shock stability and thermal conductivity of CA₆ porous ceramics were systematically studied. The pores of CA₆ porous ceramics are mainly formed by the burning loss of PMMA microspheres and the decomposition of organic matter. Adding an appropriate amount of PMMA microspheres as pore-forming agent has a positive effect on the thermal shock stability of CA₆ porous ceramics. When the amount of pore-forming agent is 15 wt%, the volume density of CA₆ porous ceramics is 1.33 g/cm³, the porosity is 63%, the flexural strength is 13.9 MPa, the thermal shock times can reach 9 times, and the thermal conductivity is 0.293 W/(m·K), which can meet the application in refractory, ceramics or high temperature cement industries.     

Effect of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-ZrO<Subscript>2</Subscript> xerogel support on hydrogen production by steam reforming of LNG over Ni/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-ZrO<Subscript>2</Subscript> catalyst

An Al₂O₃-ZrO₂ xerogel (AZ-SG) was prepared by a sol-gel method for use as a support for a nickel catalyst. The Ni/AZ-SG catalyst was then prepared by an impregnation method, and was applied to hydrogen production by steam reforming of LNG. A nickel catalyst supported on commercial alumina (A-C) was also prepared (Ni/A-C) for comparison. The hydroxyl-rich surface of the AZ-SG support increased the dispersion of nickel species on the support during the calcination step. The formation of a surface nickel aluminate-like phase in the Ni/AZ-SG catalyst greatly enhanced the reducibility of the Ni/AZ-SG catalyst. The ZrO₂ in the AZ-SG support increased the adsorption of steam onto the support and the subsequent spillover of steam from the support to the active nickel sites in the Ni/AZ-SG catalyst. Both the high surface area and the well-developed mesoporosity of the Ni/AZ-SG catalyst improved the gasification of adsorbed surface hydrocarbons in the reaction. In the steam reforming of LNG, the Ni/AZ-SG catalyst showed a better catalytic performance than the Ni/A-C catalyst. Moreover, the Ni/AZ-SG catalyst showed strong resistance toward catalyst deactivation.     

Synthesis and properties of flux-cast refractories in the Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-MgO-B<Subscript>2</Subscript>O<Subscript>3</Subscript> system

Details are given of the synthesis and testing of flux-cast refractory materials in the alumina-rich region of the Al₂O₃-MgO-B₂O₃ system; XRD and petrography indicate that the main structure-forming phases are corundum and magnesian spinel. In subordinate amounts there are the boroaluminate 9Al₂O₃·2B₂O₃ and the previously unknown compound 4Al₂O₃·MgO·2B₂O₃, whose composition has been established by microprobe analysis. Corrosion tests showed that three-component systems containing magnesium and boron oxides at levels of 5–10% do not increase the corrosion resistance of refractories in molten sodium-calcium-silicate glass and electrovacuum borosilicate glass. __________ Translated from Novye Ogneupory, No. 3, pp. 161–163, March, 2008.     

Viscosity affected by nanoparticle aggregation in Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-water nanofluids

An investigation on viscosity was conducted 2 weeks after the Al₂O₃-water nanofluids having dispersants were prepared at the volume concentration of 1-5%. The shear stress was observed with a non-Newtonian behavior. On further ultrasonic agitation treatment, the nanofluids resumed as a Newtonian fluids. The relative viscosity increases as the volume concentrations increases. At 5% volume concentration, an increment was about 60% in the re-ultrasonication nanofluids in comparison with the base fluid. The microstructure analysis indicates that a higher nanoparticle aggregation had been observed in the nanofluids before re-ultrasonication.     

Europium(II) in glasses of the Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript>-MnO-Eu<Subscript>2</Subscript>O<Subscript>3</Subscript> system

Triply and doubly charged states of europium are revealed by ¹⁵¹Eu Mössbauer spectroscopy in the structure of glasses of the composition (mol %) 19.5Al₂O₃, 31.5SiO₂, 26.5MnO, and 22.5Eu₂O₃. The isomer shifts in the Mössbauer spectra of Eu³⁺ and Eu²⁺ ions in the structure of glasses differ from the isomer shifts in the spectra of the Eu₂O₃ and EuO compounds. This difference is explained by the fact that the electron density at ¹⁵¹Eu nuclei is affected by the manganese and aluminum atoms, which are not bound directly to the europium atoms. The broadening of the spectra of the Eu²⁺ ions in glasses is caused by the nonuniform isomer shift.     

Uniform color coating of multilayered TiO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> films by atomic layer deposition

Thin film optics, based on light interference characteristics, are attracting increasing interest because of their ability to enable a functional color coating for various applications in optical, electronic, and solar industries. Here, we report on the dependence of coloring characteristics on single-layer TiO₂ thicknesses and alternating TiO₂/Al₂O₃ multilayer structures prepared by atomic layer deposition (ALD) at a low growth temperature. The ALD TiO₂ and Al₂O₃ thin films were studied at a low growth temperature of 80°C. Then, the coloring features in the single-layer TiO₂ and alternating TiO₂/Al₂O₃ multilayers using both the ALD processes were experimentally examined on a TiN/cut stainless steel sheet. The Essential Macleod software was used to estimate and compare the color coating results. The simulation results revealed that five different colors of the single TiO₂ layers were shown experimentally, depending on the film thickness. For the purpose of highly uniform pink color coating, the film structures of TiO₂/Al₂O₃ multilayers were designed in advance. It was experimentally demonstrated that the evaluated colors corresponded well with the simulated color spectrum results, exhibiting a uniform pink color with wide incident angles ranging from 0° to 75°. This article advances practical applications requiring highly uniform color coatings of surfaces in a variety of optical coating areas with complex topographical structures.     

Synthetic spinels of the system MgO-Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>

Synthetic spinels of the system MgO-Cr₂O₃-Al₂O₃-Fe₂O₃ are considered and the desirability of organizing their production for the refractory industry is demonstrated. Translated from Novye Ogneupory, No. 6, pp. 32–35, June 2008.     

Maximization of total surface area of Pt-SnO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst by the Taguchi method

The maximization of the total surface area of Pt-SnO₂/Al₂O₃ catalyst was studied by using the Taguchi method of experimental design. The catalysts were prepared by sol-gel method. The effects of HNO₃, H₂O and aluminum nitrate concentrations and the stirring rate on the total surface area were studied at three levels of each. L₉ orthogonal array leading nine experiments was used in the experimental design. The parameter levels that give maximum total surface area were determined and experimentally verified. In the range of conditions studied it was found that, medium levels of HNO₃ and H₂O concentration and lower levels of aluminum nitrate concentration and stirring rate maximize the total surface area.     

The Structure of Fusion-Cast High-Chrome Oxide Refractories in the Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> - MgO - Al<Subscript>2</Subscript>O<Subscript>3</Subscript> System

The phase composition and structure of fusion-cast refractories composed of 57.0 – 84.2% Cr₂O₃, 4.3 – 36.1% MgO, 2.0 – 9.7% Al₂O₃, and 2.4 – 6.9% SiO₂ have been studied by petrographic and x-ray spectral microprobe analysis methods. Refractories high in MgO with modulus M = (Cr₂O₃ +Al₂O₃)/MgO = 1.64 – 3.1 are shown to consist of spinel phase Mg(Cr, Al)₂O₄ and silicate glass. Refractory materials (80.8 – 84.2% Cr₂O₃, 4.3 – 4.7% MgO, 2.0 – 9.7% Al₂O₃, and 2.7 – 6.9% SiO₂ with M = 18.7 – 20.2) are three-phase systems composed of spinel, escolaite, and glass phase. These materials, owing to their high corrosion resistance, have promising potentiality for practical applications.__________Translated from Novye Ogneupory, No. 12, pp. 69 – 74, December, 2004.     

Analysis of the formation of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> + Fe nanocomposites

The formation of Al₂O₃ + Fe nanocomposites (in the range 0–20 wt % Fe) in the course of three sequential processes, such as dispersion, compaction, and sintering at a temperature of 1573 K, is investigated. It is revealed that the sintering is accompanied by the formation of the spinel phase at interfaces. It is demonstrated that the composition of the sintered samples corresponds to an equilibrium composition at a temperature of approximately 1073 K and that the spinel phase serves as a barrier layer preventing oxidation of iron     

Synthesis and properties of the composite ceramics from nanocrystalline Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-30% Y<Subscript>0.1</Subscript>Zr<Subscript>0.9</Subscript>O<Subscript>2</Subscript> prepared from a water-alcohol solution

The hydrogel of the mixed oxide Al₂O₃-30% Y_0.1Zr_0.9O₂ was prepared by precipitation of ammonia from a water-alcohol mixture (1 : 5). The Al₂O₃-30% Y_0.1Zr_0.9O₂ compound thus synthesized was characterized using differential scanning calorimetry, transmission electron microscopy, and the BET adsorption method. The obtained sample consisted of spherical particles with an average size of 16–20 nm and a specific surface area of 167 m²/g. The Al₂O₃-30% Y_0.1Zr_0.9O₂ powder was pressed at 300 MPa and then calcinated at 1600°C for 2 h in air. The topographic and structural features of the prepared ceramics were determined using atomic force microscopy and X-ray electron probe microanalysis. The porosity, the Vickers microhardness, and the tensile strength were determined by mercury porometry.     

Preparation and application of zeolite beta with super-low SiO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> ratio

This paper presents the direct synthesis of super-low SiO₂/Al₂O₃ ratio zeolite beta molecular sieve through a novel route, by which some of aluminium species are added during crystaling process. The IR results show that with the increase of aluminium content in the framework, the frequency of the band in the range of framework vibration (1060–1090 cm⁻¹) shifts to the lower wave-number; the BET surface-area decreases and the basicity of zeolite becomes stronger. In a second step, new adsorbents were obtained by solid-state ion exchanging zeolite beta with Cu(I), Ag(I) cations. The deep-desulfurization (sulfur levels of <1 ppmw) tests were performed using fixed-bed adsorption technique, the sulfur content of the treated and untreated gasoline was analyzed by microcoulometry. The experimental results show that the desulfurization performance of sorbents decreases in order: Cu(I)beta > Ag(I)beta > Na-beta. The best sorbent, Cu(I)beta, has breakthrough adsorption capacities of 0.236 mmolS/g of sorbent for model gasoline.     

Structural evolution of hierarchical porous NiO/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> composites and their application for removal of dyes by adsorption

Hierarchical porous NiO/Al₂O₃ composites were successfully prepared by two-steps. First, the core-shell structured Al₂O₃ microspheres were prepared via a template-free hydrothermal route using KAl(SO₄)₂·12H₂O and Al₂(SO₄)₃·18H₂O as aluminum source. Then, the NiO/Al₂O₃ composites with micro- and nano-hierarchical structures were prepared by a hydrothermal method combining the subsequent calcination process. The obtained characterization result presented that the morphology of hierarchical Al₂O₃ microsphere tuned to irregular platelets by simply varying Ni/Al ratios. The BET analysis showed that the special surface area from 52.12m² g^?1 to 214.8m² g^?1 after two hydrothermal complex process. Effects of Ni/Al ratio, adsorbent dosage, Congo red (CR) concentration, coexisting ions, adsorption time and temperature were investigated. The obtained results indicated that NiO/Al₂O₃ composite had the high adsorption efficiency (99.6%) and great adsorption capacity (186.9mg g^?1) under the optimum conditions. The adsorption isotherm and kinetics data were found to be well fitted and in good agreement with the Langmuir isotherm model and pseudo-second order model, respectively. The hierarchical porous NiO/Al₂O₃ composites presented remarkably higher adsorption efficiency during five recycling, which showed their potential as the highly efficient adsorbent for removal of CR in wastewater.     

Enhanced cyclic stability of CO<Subscript>2</Subscript> adsorption capacity of CaO-based sorbents using La<Subscript>2</Subscript>O<Subscript>3</Subscript> or Ca<Subscript>12</Subscript>Al<Subscript>14</Subscript>O<Subscript>33</Subscript> as additives

To improve the stability of CaO adsorption capacity for CO₂ capture during multiple carbonation/calcination cycles, modified CaO-based sorbents were synthesized by sol-gel-combustion-synthesis (SGCS) method and wet physical mixing method, respectively, to overcome the problem of loss-in-capacity of CaO-based sorbents. The cyclic CaO adsorption capacity of the sorbents as well as the effect of the addition of La₂O₃ or Ca₁₂Al₁₄O₃₃ was investigated in a fixed-bed reactor. The transient phase change and microstructure were characterized by X-ray diffraction (XRD) and field emission scanning electron microscopy (FSEM), respectively. The experimental results indicate that La₂O₃ played an active role in the carbonation/calcination reactions. When the sorbents were made by wet physical mixing method, CaO/Ca₁₂Al₁₄O₃₃ was much better than CaO/La₂O₃ in cyclic CO₂ capture performance. When the sorbents were made by SGCS method, the synthetic CaO/La₂O₃ sorbent provided the best performance of a carbonation conversion of up to 93% and an adsorption capacity of up to 0.58 g-CO₂/g-sorbent after 11 cycles.     

Thermal conductivity and viscosity measurements of ethylene glycol-based Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanofluids

The dispersion and stability of nanofluids obtained by dispersing Al₂O₃ nanoparticles in ethylene glycol have been analyzed at several concentrations up to 25% in mass fraction. The thermal conductivity and viscosity were experimentally determined at temperatures ranging from 283.15 K to 323.15 K using an apparatus based on the hot-wire method and a rotational viscometer, respectively. It has been found that both thermal conductivity and viscosity increase with the concentration of nanoparticles, whereas when the temperature increases the viscosity diminishes and the thermal conductivity rises. Measured enhancements on thermal conductivity (up to 19%) compare well with literature values when available. New viscosity experimental data yield values more than twice larger than the base fluid. The influence of particle size on viscosity has been also studied, finding large differences that must be taken into account for any practical application. These experimental results were compared with some theoretical models, as those of Maxwell-Hamilton and Crosser for thermal conductivity and Krieger and Dougherty for viscosity.     

Influences of phase transition and microstructure on dielectric properties of Bi<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>Zr<Subscript>1-x</Subscript>Ti<Subscript>x</Subscript>O<Subscript>3</Subscript> ceramics

Bismuth sodium zirconate titanate ceramics with the formula Bi_0.5Na_0.5Zr_1-xTi_xO₃ [BNZT], where x = 0.3, 0.4, 0.5, and 0.6, were prepared by a conventional solid-state sintering method. Phase identification was investigated using an X-ray diffraction technique. All compositions exhibited complete solubility of Ti⁴⁺ at the Zr⁴⁺ site. Both a decrease of unit cell size and phase transition from an orthorhombic Zr-rich composition to a rhombohedral crystal structure in a Ti-rich composition were observed as a result of Ti⁴⁺ substitution. These changes caused dielectric properties of BNZT ceramics to enhance. Microstructural observation carried out employing SEM showed that average grain size decreased when addition of Ti increased. Grain size difference of BNZT above 0.4 mole fraction of Ti⁴⁺ displayed a significant increase of dielectric constant at room temperature.