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.     

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.     

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.     

Chemical and electrochemical characterization of TiO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> atomic layer depositions on AZ-31 magnesium alloy

In this study, innovative TiO₂/Al₂O₃ mono/multilayers were applied by atomic layer depositions (ALD) on ASTM-AZ-31 magnesium/aluminum alloy to enhance its well-known scarce corrosion resistance. Four different configurations of ALD layers were tested: single TiO₂ layer, single Al₂O₃ layer, Al₂O₃/TiO₂ bilayer and Al₂O₃/TiO₂/Al₂O₃/TiO₂ multilayer deposited using Al[(CH₃)]₃ (trimethylaluminum, TMA), and TiCl₄ and H₂O precursors. All depositions were performed at 120°C to obtain an amorphous-like structure of both oxide layers. The four coatings were then investigated using different techniques, such as scanning electron microscope (SEM), stylus profilometer, glow discharge optical emission spectrometry (GDOES) and polarization curves in 0.05-M NaCl solution. The thickness of all the coatings was around 100 nm. The layers compositions were successfully investigated by the GDOES technique, although obtained data seem to be affected by substrate roughness and differences in sputtering rates between ceramic oxides and metallic magnesium alloy. Corrosion resistance showed to be strongly enhanced by the nanometric coatings, giving lower corrosion current densities in 0.05-M NaCl media with respect to the uncoated substrate (from 10⁻⁴ to 10⁻⁶ A/cm² for the single layers and from 10⁻⁴ to 10⁻⁸ A/cm² for the bi- and multilayers). All polarization curves on coated samples also showed a passive region, wider for the bi-layer (from −0.58 to −0.43 V with respect to Ag/AgCl) and multilayer (from −0.53 to −0.38 V with respect to Ag/AgCl) structures.     

Formation of La<Subscript>2</Subscript>Ti<Subscript>2</Subscript>O<Subscript>7</Subscript> crystals from amorphous La<Subscript>2</Subscript>O<Subscript>3</Subscript>-TiO<Subscript>2</Subscript> powders synthesized by the polymerized complex method

Amorphous La₂O-TiO₂ powders were synthesized by the polymerized complex (PC) method. The activation energies for crystallization and grain growth of La₂Ti₂O₇ from these precursors were determined from results of XRD and DTA and compared with those for La₂Ti₂O₇ precursors by the conventional solid-state reaction (SSR). Activation energy of grain growth of La₂Ti₂O₇ in PC-sample was determined to be 7.1 kJ/mol while that of SSR sample was 14.8 kJ/mol. The energy required for the phase transformation from amorphous PC sample to layered perovskite was 432 kJ/mol, while the SSR sample did not show this transition below 900‡C. It was clearly demonstrated that the La₂Ti₂O₇ crystals were formed at a lower temperature and they grew in size faster in the sample prepared by the PC method relative to the sample prepared by the SSR method. Mixing of elements in molecular level in PC preparation appeared responsible for these differences.     

Properties of unsupported MoS<Subscript>2</Subscript> species produced in the preparation of MoS<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> using a sonochemical method

Unsupported MoS₂ particles, which were produced in the preparation of MoS₂/Al₂O₃ using a sonochemical method, were successfully separated from the prepared sample catalyst by adding oleylamine as an agent for dispersing the unsupported particles. The fraction of the unsupported MoS₂, which was estimated based on Mo balance, varied between 0.03 and 0.4, independent of the Mo loading levels investigated (6–54 wt% of Mo). The activity of the unsupported MoS₂ for the hydrodesulfurization of dibenzothiophene was nearly the same as that of the Al₂O₃-supported MoS₂, indicating that the activity of the prepared catalyst was not affected by the presence of the unsupported MoS₂ particles.     

Oxidative reforming of methane on structured Ni-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/cordierite catalysts

The catalytic properties of Ni/Al₂O₃ composites supported on ceramic cordierite honeycomb monoliths in oxidative methane reforming are reported. The prereduced catalyst has been tested in a flow reactor using reaction mixtures of the following compositions: in methane oxidation, 2–6% CH₄, 2–9% O₂, Ar; in carbon dioxide and oxidative carbon dioxide reforming of methane, 2–6% CH₄, 6–12% CO₂, and 0–4% O₂, and Ar. Physicochemical studies include the monitoring of the formation and oxidation of carbon, the strength of the Ni-O bond, and the phase composition of the catalyst. The structured Ni-Al₂O₃ catalysts are much more productive in the carbon dioxide reforming of methane than conventional granular catalysts. The catalysts performance is made more stable by regulating the acid-base properties of their surface via the introduction of alkali metal (Na, K) oxides to retard the coking of the surface. Rare-earth metal oxides with a low redox potential (La₂O₃, CeO₂) enhance the activity and stability of Ni-Al₂O₃/cordierite catalysts in the deep and partial oxidation and carbon dioxide reforming of methane. The carbon dioxide reforming of methane on the (NiO + La₂O₃ + Al₂O₃)/cordierite catalyst can be intensified by adding oxygen to the gas feed. This reduces the temperature necessary to reach a high methane conversion and does not exert any significant effect on the selectivity with respect to H₂.     

Catalytic cracking of isobutane over HZSM-5, FeHZSM-5 and CrHZSM-5 catalysts with different SiO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> ratios

Several systems of HZSM-5, FeHZSM-5 and CrHZSM-5 zeolite catalysts with different ratios of SiO₂/Al₂O₃ (25,38,50,80, and 150) were prepared and they were characterized by means of X-ray diffraction (XRD), UV–Vis, NH₃-TPD and BET techniques. The results indicated that, compared with uncalcined HZSM-5 zeolites, the total acid amounts, acidic site density and acidic strength of HZSM-5, FeHZSM-5 and CrHZSM-5 zeolite catalysts obviously decreased, while those of weak acid amounts obviously enhanced with the decrease of SiO₂/Al₂O₃ molar ratio. When the ratio of SiO₂/Al₂O₃ is less than 50, the three systems of HZSM-5, FeHZSM-5 and CrHZSM-5 zeolite catalysts with same ratio of SiO₂/Al₂O₃ gave similar and high isobutane conversions. However, when the ratio of SiO₂/Al₂O₃ was equal to or greater than 80, these three systems of catalysts possessed different altering tendencies of isobutane conversions, thus their isobutene conversions were different. High yields of light olefins were obtained over the FeHZSM-5 and CrHZSM-5 zeolite catalysts with high ratio of SiO₂/Al₂O₃ (≥80). The ratio of SiO₂/Al₂O₃ has large effects on the surface area, and acidic characteristics of HZSM-5, FeHZSM-5 and CrHZSM-5 zeolites catalysts, and thus further affect their catalytic performances for isobutane cracking. That is the nature of SiO₂/Al₂O₃ ratio effect on the catalytic performances.     

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.     

Synthesis and optical property of one-dimensional spinel ZnMn<Subscript>2</Subscript>O<Subscript>4</Subscript> nanorods

Spinel zinc manganese oxide (ZnMn₂O₄) nanorods were successfully prepared using the previously synthesized α-MnO₂ nanorods by a hydrothermal method as template. The nanorods were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, UV-Vis absorption, X-ray photoelectron spectroscopy, surface photovoltage spectroscopy, and Fourier transform infrared spectroscopy. The ZnMn₂O₄ nanorods in well-formed crystallinity and phase purity appeared with the width in 50-100 nm and the length in 1.5-2 μm. They exhibited strong absorption below 500 nm with the threshold edges around 700 nm. A significant photovoltage response in the region below 400 nm could be observed for the nanorods calcined at 650 and 800°C.     

Promoting Effect of Triglyme on Lean NO<Subscript>x</Subscript> Reduction Over Ag/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

Abstract  

The highly oxygenated hydrocarbon triethylene glycol dimethyl ether or triglyme (CH₃O–(C₂H₄O–)₃CH₃) was found to efficiently reduce NO_x under lean conditions over Ag/Al₂O₃, but gave a low NO_x conversion over Cu-ZSM-5. Furthermore, triglyme showed an extraordinary promoting effect when added together with propene as reducing agent for NO_x over Ag/Al₂O₃ at low temperature. This is most likely due to that triglyme promotes the activation of propene.     

Electrical properties of lead-free 0.98(Na<Subscript>0.5</Subscript>K<Subscript>0.5</Subscript>)NbO<Subscript>3</Subscript>-0.02Ba(Zr<Subscript>0.52</Subscript>Ti<Subscript>0.48</Subscript>)O<Subscript>3</Subscript> piezoelectric ceramics by optimizing sintering temperature

Lead-free 0.98(Na_0.5K_0.5)NbO₃-0.02Ba(Zr_0.52Ti_0.48)O₃ [0.98NKN-0.02BZT] ceramics were fabricated by the conventional mixed oxide method with sintering temperature at 1,080°C to 1,120°C. The results indicate that the sintering temperature obviously influences the structural and electrical properties of the sample. For the 0.98NKN-0.02BZT ceramics sintered at 1,080°C to 1,120°C, the bulk density increased with increasing sintering temperature and showed a maximum value at a sintering temperature of 1,090°C. The dielectric constant, piezoelectric constant [d ₃₃], electromechanical coupling coefficient [k _p], and remnant polarization [P _r] increased with increasing sintering temperature, which might be related to the increase in the relative density. However, the samples would be deteriorated when they are sintered above the optimum temperature. High piezoelectric properties of d ₃₃ = 217 pC/N, k _p = 41%, dielectric constant = 1,951, and ferroelectric properties of P _r = 10.3 μC/cm² were obtained for the 0.98NKN-0.02BZT ceramics sintered at 1,090°C for 4 h.     

An investigation into the conversion of In<Subscript>2</Subscript>O<Subscript>3</Subscript> into InN nanowires

Straight In₂O₃ nanowires (NWs) with diameters of 50 nm and lengths ≥2 μm have been grown on Si(001) via the wet oxidation of In at 850°C using Au as a catalyst. These exhibited clear peaks in the X-ray diffraction corresponding to the body centred cubic crystal structure of In₂O₃ while the photoluminescence (PL) spectrum at 300 K consisted of two broad peaks, centred around 400 and 550 nm. The post-growth nitridation of In₂O₃ NWs was systematically investigated by varying the nitridation temperature between 500 and 900°C, flow of NH₃ and nitridation times between 1 and 6 h. The NWs are eliminated above 600°C while long nitridation times at 500 and 600°C did not result into the efficient conversion of In₂O₃ to InN. We find that the nitridation of In₂O₃ is effective by using NH₃ and H₂ or a two-step temperature nitridation process using just NH₃ and slower ramp rates. We discuss the nitridation mechanism and its effect on the PL.     

Refractive index and compressibility of the KAlSi<Subscript>3</Subscript>O<Subscript>8</Subscript> glass at pressures up to 6.0 GPa

The refractive index of potassium aluminosilicate glass of the KAlSi₃O₈ composition in the pressure range up to 6.0 GPa has been measured using a polarizing interference microscope and an apparatus with diamond anvils. The changes in the relative density, which characterize the compressibility of the K₂O · Al₂O₃ · 6SiO₂ glass, have been estimated in the pressure range under investigation from the measured refractive indices within the framework of the theory of photoelasticity. The results have been compared with the data previously obtained for the Na₂O · Al₂O₃ · 6SiO₂ glass. Although the molar contents of Al₂O₃ and M ₂O (where M = K or Na) are identical in these glasses, the KAlSi₃O₈ glass exhibits a higher compressibility, which agrees with the lower degree of depolymerization of this glass as compared to that observed in the NaAlSi₃O₈ glass. The pressure derivative of the bulk modulus K′ _t , which is calculated from the Birch-Murnaghan equation for the KAlSi₃O₈ glass (K′ _t = 7–9), is higher than that for the NaAlSi₃O₈ glass (K′ _t = 5.5–6.0). An increase in the pressure derivative of the bulk modulus K′ _t upon replacement of the Na⁺ cations by the K⁺ cations is explained by the inhibition of compression of the large K⁺ cations, which are located in cavities and have a considerably larger orbital radius than the Na+ cations. This manifests itself in the fact that the curves describing the dependences of the change in the relative density (d − d0)/d (compressibility) on the pressure P for the KAlSi₃O₈ and NaAlSi₃O₈ glasses converge at pressures above 4.0 GPa.     

Combustion synthesis of some compounds in the Li<Subscript>2</Subscript>O-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> system

At least four compounds, viz. LiAlO₂, LiAl₅O₈, Li₅AlO₄ and Li₂Al₄O₇, are known in the Li₂O-Al₂O₃ system. These compounds are important for several technological applications. Combustion synthesis of these compounds using urea as a fuel was attempted. LiAlO₂ and LiAl₅O₈ could be successfully prepared by choosing the starting materials in required stoichiometric ratios. Li₂Al₄O₇ was not obtained as a pure phase; γ-LiAlO₂ was formed as an impurity phase. Li₅AlO₄ could not be prepared by combustion process. Some phosphors based on these aluminates could also be prepared. Activation of these aluminates with Fe³⁺, Mn⁴⁺, Cu⁺, etc. was successfully achieved. Excitation and emission spectra for LiAl₅O₈: Fe³⁺, LiAl₅O₈: Mn²⁺, and Li₂Al₄O₇: Cu⁺ are reported.     

Study on the properties of Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-BaO lead-free glass using in the electronic pastes

The Sb₂O₃ doping lead-free glass in Bi₂O₃-B₂O₃-BaO ternary system were prepared in the composition of several different subsystem, and the glass powder was produced through the process of water quenching. Glass transition temperatures (T _g ), glass soften temperatures(T _s ), the volume resistivity (ρ) in the temperature range of 80–200°C, and linear thermal coefficients of expansion in the temperatures range of 25–300°C (α_25–300) were measured for subsystems along with the different ratio of Bi₂O₃, B₂O₃ and BaO. For these subsystems, T _g ranged from 458 to 481°C, and T _s ranged from 490 to 512°C, both decreasing with the increasing of Bi₂O₃/B₂O₃ ratio, and increasing with the increasing of BaO/B₂O₃ ratio. The measured α_25–300 ranged from 65.3 to 76.3 × 10⁻⁷ K⁻¹, with values increasing with increasing Bi₂O₃/B₂O₃ and BaO/B₂O₃ ratio. The volume resistivity remains at a high standards, which may caused by it’s non-alkali composition, and it fluctuated from 10¹³ to 10¹¹ Ω cm with the temperature varied from 80–200°C. The structure of Bi₂O₃-B₂O₃-BaO ternary leadfree glass system was mearsured by FT-IR. The IR studies indicate that these glasses are made up of [BiO₆], [BO₃], and [BO₄] basic structural units, and it appears that Ba²⁺ acts as a glass-modifier in this ternary system, but the Bi³⁺ has entered the glass network when it is in relative high content so as to change the α_25–300, T _s and T _g .     

CO oxidation from syngas (CO and H<Subscript>2</Subscript>) using nanoporous Pt/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst

The concept of “waste-to-wealth” is spreading awareness to prevent global warming and recycle the restrictive resources. To contribute towards sustainable development, hydrogen energy is obtained from syngas (CO and H₂) generated from waste gasification, followed by CO oxidation and CO₂ removal. In H₂ generation, it is key to produce more purified H₂ from syngas using heterogeneous catalysts. In this respect, we prepared Pt/Al₂O₃ catalyst with nanoporous structure using precipitation method, and compared its catalytic activity with commercial alumina (Degussa). Based on the results of XRD and TEM, it was found that metal particles did not aggregate on the alumina surface and showed high dispersion. Optimum condition for CO conversion was 1.5 wt% Pt loaded on Al₂O₃ support, and pure hydrogen was obtained after removal of CO₂ gas.     

Phase evolution during mechanochemical coreduction of V<Subscript>2</Subscript>O<Subscript>5</Subscript> and TiO<Subscript>2</Subscript> with A

The direct preparation of V-Ti solid solution alloy by coreduction of V₂O₅ and TiO₂ with Al in an attritor mill was investigated. The reduction of V₂O₅ with Al is highly exothermic, whereas reduction of TiO₂ with Al is not sufficiently exothermic for a self-sustaining reaction. A range of compositions of a mixture of V₂O₅ and TiO₂ can be so chosen as to make the overall reduction of V₂O₅ and TiO₂ with Al sufficiently exothermic for a self-sustaining reaction. Initial studies were done to identify the reaction products obtained by reducing V₂O₅ with Al. The reaction yielded the intermetallic phase (Al₃V), V, and Al₂O₃. SEM images indicated melting and solidification of the phases, leading to agglomeration. Further experiments involved mixing appropriate amounts of TiO₂ with V₂O₅ and reducing the mixture with Al. XRD data for products showed the presence of V, V₅Al₈, and Al₂O₃. X-Ray Florescence (XRF) analysis and energy dispersive analyzer (EDAX) of SEM sample images indicated the formation of V-Ti solid solution. Microstructure of the milled charges taken out prior to reaction initiation indicated morphology change in Al powder and agglomeration/segregation of reactants. As a result, the reaction of V₂O₅ with the excess Al at certain regions also promoted the formation of vanadium aluminide.     

Thermomechanical properties of refractory materials of AL<Subscript>2</Subscript>O<Subscript>3</Subscript>–Si<Subscript>3</Subscript>N<Subscript>4</Subscript>–C compositions based on acpb after impregnation with a sol-gel composition

Comparative characteristics are presented for the physicomechanical properties and oxidation resistance of refractory materials of Al₂O₃–Si₃N₄–C composition based on an ACPB for the original materials (fired at 1400°C) and after impregnation with a sol-gel composition and heat treatment at 800°C. Areduction in material porosity, increase in strength and reduction in carbon burn-off are due to development of a glassy phase in the pore space and on graphite flakes due to SiO₂formation with thermal destruction of the organosilicon substance.     

Combined Steam and Carbon Dioxide Reforming of Methane on Ni/MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript>: Effect of CeO<Subscript>2</Subscript> Promoter to Catalytic Performance

Abstract  

The catalytic performance during combined steam and carbon dioxide reforming of methane (SCR) was investigated on Ni/MgAl₂O₄ catalyst promoted with CeO₂. The SCR catalyst was prepared by co-impregnation method using nickel and cerium metal precursors on hydrotalcite-like MgAl₂O₄ support. In terms of catalytic activity and stability, CeO₂-promoted Ni/MgAl₂O₄ catalyst is superior to Ni–CeO₂/Al₂O₃ or Ni/MgAl₂O₄ catalysts because of high resistance to coke formation and suppressed aggregation of nickel particles. The role of CeO₂ on Ni/MgAl₂O₄ catalyst was elucidated by carrying out the various characterization methods in the viewpoint of the aggregation of nickel particles and metal-support interactions. The observed superior catalytic performance on CeO₂-promoted Ni/MgAl₂O₄ catalyst at the weight ratio of MgO/Al₂O₃ of 3/7 seems to be closely related to high dispersion and low aggregation of active metals due to their strong interaction with the MgAl₂O₄ support and the adjacent contact of Ni and CeO₂ species. The CeO₂ promoter also plays an important role to suppress particle aggregation by forming an appropriate interaction of NiO–CeO₂ as well as Ni–MgAl₂O₄ with the concomitant enhancement of mobile oxygen content.