Catalytic decomposition of N2O over supported rhodium catalysts: high activities of Rh/USY and Rh/Al2O3 and the effect of Rh precursors

The catalytic decomposition of nitrous oxide to nitrogen and oxygen has been studied over Al₂O₃-supported and zeolite-supported Rh catalysts. The activities of Rh/Al₂O₃ and Rh/USY (ultrastable Y zeolite) catalysts prepared from Rh(NO₃)₃ were higher than those of Rh/ZSM-5 and Rh/ZnO reported in the literature, while the activity of a Rh/Al₂O₃ catalyst prepared from RhCl₃ was suppressed severely in spite of the high H/Rh and CO/Rh values. The catalytic activity of N₂O decomposition was sensitive not only to the Rh dispersion but also to the preparation variables such as the Rh precursors and the supports used. This revised version was published online in July 2006 with corrections to the Cover Date.     

0.73ZrTi2O6–0.27MgNb2O6 microwave dielectric ceramics modified by Al2O3 addition

0.73ZrTi₂O₆–0.27MgNb₂O₆ ceramics with various Al₂O₃ contents (0‐2.0 wt%) were prepared by conventional ceramic route. The effects of Al₂O₃ on the phase composition, microstructure, conductivity, and microwave dielectric properties were systematically investigated. The coexistence of a disordered α–PbO₂‐type phase and a rutile second phase was found in all compact ceramics with low Al₂O₃ contents (x = 0, 0.5, and 1.0 wt%), while a corundum phase was detected when Al₂O₃ additive increased to 1.5 and 2.0 wt% based on X‐ray diffraction results. With the addition of Al₂O₃, the decreased grain size of the matrix phase was observed using field‐emission scanning electron microscope, accompanied with increased resistivity and band‐gap energy. Additionally, Al₂O₃ additives efficiently improved the quality factor of the ceramics. After sintering at 1360°C for 3 hours, the ceramic with 1.0 wt% Al₂O₃ exhibited excellent microwave dielectric properties: a dielectric constant of 43.8, a quality factor of 33 900 GHz (at 6.6 GHz), and a near‐zero temperature coefficient of resonant frequency (3.1 ppm/^°C).     

Characterization of some perovskite oxides based on YBa2Cu3O7 − x in relation to their use in methanol production

The oxidized and weakly reducible perovskite oxide YBa₂Cu₃O_{7 − x} (YBCO) has been prepared as a catalyst, supported on γ‐Al₂O₃. It was further modified by (i) impregnation with Ru and Pd and (ii) cobalt incorporation via co‐precipitation. All the catalysts were either 20% (w/w) YBCO/γ‐Al₂O₃ or 2% (w/w) Ru, Pd or Co/20% (w/w) YBCO/γ‐Al₂O₃. The catalysts were characterized using temperature programmed reduction (TPR), surface area measurements and X‐ray diffraction (XRD) studies before and after various treatments. They were studied as catalysts in the pressure range 20–50 atmospheres and in the temperature range 523–573 K in an autoclave equipped with a spinning basket catalyst container. The Pd‐, Ru‐ and Co‐modified catalysts gave predominantly methanation products, along with some C₂–C₄ hydrocarbons. However the YBCO/γ‐Al₂O₃ catalyst exhibited significant methanol selectivity at 50 atmospheres and at 523 K X‐ray diffraction studies revealed the presence of Cu(0), Cu(I) and Cu(II) after reduction and the species Cu(0) and Cu(I) are probably essential to CH₃OH production. © 2000 Society of Chemical Industry     

Surface‐Functionalized White Sapphire α‐Al2O3 Platelets as Nanofillers for Vinylester Composites and Heavy Duty Anchoring Systems

Synthetic α‐Al₂O₃ platelets, also referred to as corundum and white sapphire, represent attractive fillers improving the mechanical properties of vinylester‐based chemical anchoring systems. Even in the absence of coupling agents, as verified by scanning electron microscopic (SEM) analyses of fracture surfaces, α‐Al₂O₃ platelets of 200 nm thickness and 5–10 µm size are uniformly dispersed in vinylester resins which are cured by free radical polymerization at room temperature. With increasing content of ultrahard α‐Al₂O₃ platelets (0–40 wt%) the Young's modulus of α‐Al₂O₃ platelet/vinylester composites increases from 3200 to 9000 MPa. However, 1–5 wt% 3‐methacryloyloxypropyl‐trimethoxysilane (MPS) as coupling agent, added to the vinylester resin or preferably used to functionalize α‐Al₂O₃ surfaces in a filler pretreatment step, improves elongation at break (+50%) without sacrificing high stiffness and strength. The X‐ray photoelectron spectroscopy (XPS) analysis confirms the successful surface‐functionalization of α‐Al₂O₃ platelets by using pretreatments with MPS in toluene, acidified ethanol/water or tetrahydrofuran, respectively. The MPS filler pretreatment simultaneously enhances tensile strength (+22%), elongation at break (+50%), and Young's modulus (+12%) as compared to composites containing unmodified filler. According to SEM analyses of composite fracture surfaces, MPS‐mediated functionalization affords significantly improved interfacial adhesion between α‐Al₂O₃ platelets and the polymer matrix.

     

Coupled Experimental and Thermodynamic Optimization of the Na2O–FeO–Fe2O3–Al2O3 System: Part 1. Phase Diagram Experiments

As part of the complete thermodynamic modeling of the Na₂O–FeO–Fe₂O₃–Al₂O₃ system, the Na₂O–FeO–Fe₂O₃–Al₂O₃ phase diagrams in air (1583 and 1698 K) and at Fe saturation (1573 and 1673 K) were investigated using the quenching method followed by Electron Probe Micro‐Analyzer (EPMA) and X‐ray Diffraction (XRD) phase analysis. General features of the phase diagrams in this system were well revealed for the first time. A complete meta‐oxide solid solution between NaAlO₂ and NaFeO₂ was observed. An extensive solid solution of Na₂(Al,Fe)₁₂O₁₉ Na‐β?‐alumina was found and the existence of a miscibility gap in this solution was confirmed. Several compatibility triangles of three‐phase assemblages were also identified in air and at Fe saturation.     

Influence of Al2O3 support on the activity of Ag/Al2O3 catalysts for SCR of NO with decane

The role of the Al₂O₃ support on the activity of supported Ag catalyst towards the selective catalytic reduction (SCR) of NO with decane is elucidated. A series of Ag/Al₂O₃ catalysts were prepared by impregnation method and characterized by N₂ pore size distribution, XRD, UV–Vis, in-situ FT-IR and acidity measurement by NH₃ and pyridine adsorption. The catalytic activity differences of Ag/Al₂O₃ are correlated with different properties of Al₂O₃ supports and the active Ag species formed. 4wt% Ag supported on sol-gel prepared Al₂O₃ (Ag/Al₂O₃ (SG), showed higher NO _x conversion (65% at 400 °C), compared with the respective catalysts made from commercial Al₂O₃ (Ag/Al₂O₃ (GB), Ag/Al₂O₃ (ALO), (∼26 and 7% at 400 °C). The higher surface area, acidity and pore size distribution in sol–gel prepared Al₂O₃ (SG) results in higher NO and hydrocarbon conversion. Based on the UV–vis characterization, the activity of NO reduction is correlated to the presence of Ag_n^δ+ clusters and acidity of Al₂O₃ support was found to be one of the important parameter in promoting the formation and stabilization of Ag_n^δ+ clusters. Furthermore from pyridine adsorption results, presence of more number of Bronsted acid sites in Ag/Al₂O₃ (SG) is confirmed, which could also contribute to low temperature hydrocarbon activation and improve NO conversion. In situ FT-IR measurements revealed the higher rate of –CN and –NCO intermediate species formation over 4wt% Ag/Al₂O₃ (SG). We conclude that the physico–chemical properties of Al₂O₃ play a crucial role in NO _x conversion over Ag/Al₂O₃ catalysts. Thus, the activity of the Ag/Al₂O₃ catalyst can be tailored by using a proper type of Al₂O₃ support.     

Thermal Reaction of Cristobalite in Nano‐SiO2/α‐Al2O3 Powder Systems for Mullite Synthesis

Nanoscaled cristobalite and α‐Al₂O₃ powders were used as the starting materials for synthesizing mullite by solid‐state reaction. The thermal reaction of the cristobalite with α‐Al₂O₃ during the thermal treatment was examined. Cristobalite powder with a D₅₀ value of 430 nm was adopted to mix with α‐Al₂O₃ powders with a D₅₀ values of 230, 310, and 400 nm in a stoichiometric composition of 3Al₂O₃?2SiO₂ (71.8 wt% α‐Al₂O₃ and 28.2 wt% SiO₂). Samples for thermal reaction were prepared using uniaxial pressed from the three mixtures that showed various particle number ratios of SiO₂/Al₂O₃ due to the different particle sizes of α‐Al₂O_3. Examinations were performed by differential thermal analysis, X‐ray diffraction, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, and transmission electron microscopy techniques. The results showed that cristobalite particles amorphized during the thermal treatment, and then reacted with the α‐Al₂O₃ particle to form mullite via nucleation and growth. The amorphization temperature can be reduced by using finer‐sized α‐Al₂O₃ powders, thus leading to a lower temperature for mullite formation. Mullite crystals with a multidomain structure were observed in the α‐Al₂O₃ particle matrixes. The crystal orientation of the mullite was controlled by the α‐Al₂O₃ matrix, that is, [001] α‐Al₂O₃ → [001] mullite. These results indicate that the amorphization of cristobalite may trigger the reaction of SiO₂ with α‐Al₂O₃, initiating the nucleation of mullite. The α‐Al₂O₃ particles act as the hosts for mullite formation and determine the size of the mullite particles.     

Influence of two structural phases of Fe3O4 and γ‐Fe2O3 on the properties of polyimide/iron oxide composites

Partially aliphatic polyimide/iron oxide composites based on the poly(amic acid) from 5‐(2,5‐dioxotetrahydro‐3‐furyl)‐3‐methyl‐3‐cyclohexene‐1,2‐dicarboxylic acid anhydride and 4,4′‐oxydianiline with iron oxide in different weight percentages were obtained. The structural phases of the transition of magnetite to maghemite occurring in these composites, at different temperatures, are discussed. The physical characteristics, including magnetic, thermal, structural and morphological properties, evaluated using X‐ray diffraction, scanning electron microscopy and thermal analysis, are influenced by the interplay of the filler content and the structural changes of the composite. The X‐ray diffraction patterns of all samples show a cubic structure indexed as magnetite (Fe₃O₄) or maghemite (γ‐Fe₂O₃). Quantification of these two phases was evidenced by the Rietveld method. The electrical properties analysed under different humidity conditions evidence the potential applicability of these polyimide/iron oxide materials as humidity sensors. © 2015 Society of Chemical Industry     

Metastability in the MgAl2O4–Al2O3 System

Aluminum oxide must take a spinel form (γ‐Al₂O₃) at increased temperatures in order for extensive solid solution to form between MgAl₂O₄ and α‐Al₂O₃. The solvus line between MgAl₂O₄ and Al₂O₃ has been defined at 79.6 wt% Al₂O₃ at 1500°C, 83.0 wt% Al₂O₃ at 1600°C, and 86.5 wt% Al₂O₃ at 1700°C. A metastable region has been defined at temperatures up to 1700°C which could have significant implications for material processing and properties. Additionally, initial processing could have major implications on final chemistry.     

Phase evolution mechanism of non‐oxide bonded Al–Al2O3–MgO–ZrO2 composites at 1873 K in flowing nitrogen

In flowing nitrogen, non‐oxides such as Al₄O₄C, Al₂OC, Zr₂Al₃C₄, and MgAlON bonded Al₂O₃‐based composites were successfully prepared by a gaseous phase mass transfer pathway using aluminum, zirconia, alumina, and magnesia as raw materials at 1873 K, after an Al–AlN core‐shell structure was formed at 853 K. Resin bonded Al–Al₂O₃–MgO–ZrO₂ composites after sintering were characterized and analyzed by X‐ray diffraction (XRD), scanning electron microscope (SEM) and, energy dispersive spectrometer (EDS), and the influence of the MgO content on the sintered composites was studied. The results show that after sintering, the phase composition of the Al–Al₂O₃–ZrO₂ composite is Al₂O₃, Al₄O₄C, Al₂OC, and Zr₂Al₃C₄, while the phase composition of the Al–Al₂O₃–ZrO₂ composite with the addition of MgO 6 wt% and MgO 12 wt% is Al₂O₃, MgAlON, Al₄O₄C, Al₂OC, and Zr₂Al₃C₄ as well as Al₂O₃, MgAlON, Al₂OC, and Zr₂Al₃C₄, respectively. The addition of MgO changed the phase composition and distribution for the resin bonded Al–Al₂O₃–MgO–ZrO₂ system composites after sintering. When the added MgO content is equal to or more than 12 wt%, the Al₄O₄C in the resin bonded Al–Al₂O₃–MgO–ZrO₂ system composites is unable to exist in a stable phase.     

Statistical Optimization of the Biodiesel Production Process Using a Magnetic Core‐Mesoporous Shell KOH/Fe3O4@γ‐Al2O3 Nanocatalyst

A magnetic core‐mesoporous shell KOH/Fe₃O₄@γ‐Al₂O₃ nanocatalyst was synthesized using the Fe₃O₄@γ‐Al₂O₃ core‐shell structure as support and KOH as active component. The prepared samples were characterized by X‐ray diffraction (XRD), field‐emission scanning electron microscopy (FE‐SEM), energy‐dispersive X‐ray spectroscopy (EDS), Fourier transform infrared (FTIR), Brunauer‐Emmett‐Teller (BET), and vibrating sample magnetometry (VSM) techniques. Transesterification of canola oil to methyl esters (biodiesel) in the presence of the magnetic core‐mesoporous shell KOH/Fe₃O₄@γ‐Al₂O₃ nanocatalyst was investigated. Response surface methodology (RSM) based on the Box‐Behnken design (BBD) was employed to optimize the influence of important operating variables on the yield of biodiesel. A biodiesel yield of 97.4 % was achieved under optimum reaction conditions. There was an excellent agreement between experimental and predicted results.     

Effect of CeO2 and Al2O3 contents on Ce‐ZrO2/Al2O3 composites

Effect of CeO₂ and Al₂O₃ contents on phase composition, microstructures, and mechanical properties of Ce–ZrO₂/Al₂O₃ composites was studied. The CeO₂ content in CeO₂–ZrO₂ varied from 7 to 16 mol%, and the Al₂O₃ content in Ce‐ZrO₂/Al₂O₃ composites were 7 and 22 wt%. When CeO₂ content was ≤10 mol%, high Al₂O₃ content contributed to hinder the tetragonal‐to‐monoclinic ZrO₂ phase transformation during cooling and decrease the density of microcracks in the composites. Tetragonal ZrO₂ single‐phase was obtained in the composites with ≥12 mol% CeO₂, regardless of the Al₂O₃ content. Hardness, flexural strength, and toughness were dependent on CeO₂ and Al₂O₃ contents which were related to the microcracks, grain size, and phase transformation. The high flexural strength and toughness of the composites with 7wt% Al₂O₃ could be obtained at an optimum CeO₂ content of 12 mol%, whereas those of the composites with 22 wt% Al₂O₃ could be achieved in the wide CeO₂ content range of 8.5‐12 mol%.     

Preparation and characterization of Polyimide/Al2O3 nanocomposite film with good corona resistance

Polyimide/Al2O3 (PI/Al2O3) nanocomposite films based on pyromellitic dianhydride and 4,4′‐oxydianiline were fabricated by adding different proportions of nano‐Al₂O₃ inorganic particles via in situ polymerization. Microstructural analysis by scanning electron microscope (SEM) showed that the inorganic particles were homogenously dispersed in the PI matrix when mixed with appropriate amount of nano‐Al₂O₃. Fourier transform infrared spectroscopy and X‐ray diffraction analysis were also used to investigate the effect of nano‐Al₂O₃ on the polymerization process. The obtained composite films and pure film were characterized by thermogravimetry analysis, and the experimental results indicated that when comparing with pure film, the nanocomposite films displayed a better thermal stability than the pure one. Moreover, results also showed that the thermal stability of composite films steadily improved with increased content of nano‐Al₂O₃ particle. The electrical property test demonstrated that the composite films performed improving electrical breakdown strength and corona resistance. The microstructure changes of pure film and PI/Al₂O₃ nanocomposite films during corona aging have been analyzed by SEM. POLYM. COMPOS., 37:763–770, 2016. © 2014 Society of Plastics Engineers     

Effect of Y2O3 addition on tribological properties of plasma sprayed Al2O3-13% TiO2 coating

The effect of Y₂O₃ addition on structure, mechanical properties and tribological properties of Al₂O₃-13 wt% TiO₂ coating was investigated. The addition of 20 wt% Y₂O₃ resulted in better densification, stabilization of alpha (α) alumina phase and improvement in fracture toughness of Al₂O₃-13 wt% TiO₂ coating. Abrasive wear tests were performed over a range of loads and sliding speeds. The stabilization of α alumina phase further increased with an increase in severity of wear test conditions, as noted from X-Ray Diffraction (XRD) and X-Ray Photoelectron Spectroscopy (XPS) analysis of worn coatings. Al₂O₃-13 wt% TiO₂-20 wt% Y₂O₃ coating displayed lower friction coefficient and lower abrasive wear rate than Al₂O₃-13 wt% TiO₂ coating, which was due to synergistic effect of α alumina phase and formation of magneli phase oxide of titanium; Ti₂O₃. Friction energy map was used to rationalize observed wear rates, to identify different regimes of wear and degradation modes of coatings.     

Oxide/oxide composites in the system Cr2O3-Y2O3-Al2O3

Ceramic compacts in the systems Al₂O₃–Y₂O₃, Cr₂O₃–Y₂O₃ and Y₃(Cr_yAl_1-y)₅O₁₂ (Cr-doped YAG) were prepared by solid state reaction in calcined co-precipitated powder mixtures of appropriate compositions. Various solid-solution phases were formed, e.g. Y₃(Al_1-xCr_x)₅O₁₂, YAl_yCr_1-yO₃ and Al_2-xCr_xO₃. Composite materials in the pseudo-binary or ternary systems Al₂O₃–Y₃Al₅O₁₂, Cr₂O₃–Y₂O₃ and Y₃(Al_1–xCr_x)₅O₁₂–YAl_yCr_1–yO₃–(Al_zCr_1−z)₂O₃ were obtained by hot-pressing appropriate powder precursors at 1600–1650°C for 1 h. The microstructure of the prepared materials was studied in a scanning electron microscope with element analysis facilities. X-ray diffraction was used to reveal the phases present and their lattice parameters. The chemical compatibility of these phases was investigated. The results are discussed with a special emphasis on the solubility of Cr in the YAG structure, and on the compatibility relationship between Cr-doped YAG and its neighbouring phases. A gel-coating process for preparing Al₂O₃–YAG composites with tailored microstructures is also described.     

Structural modification associated with Al2O3 addition in oxyfluoride glasses: Thermal and mechanical properties

In this work, the effect of gradual addition of Al₂O₃ substituting SiO₂ on the structural, thermal, and mechanical properties of SiO₂–BaF₂–K₂O–GdF₃–Sb₂O₃‐based oxyfluoride glasses have been studied. The X‐ray diffraction (XRD) patterns and differential scanning calorimetric (DSC) curves indicate that there is a distinct primary crystallization corresponding to BaGdF₅ phase formation in the samples without (0AlG) and with 5 mol% substitution of Al₂O₃ (5AlG) while the sample with 10 mol% of Al₂O₃ (10AlG) does not show such crystallization event. Further, the activation energy (E_a) for fluoride crystal formation is higher for the 5AlG in comparison to the 0AlG glass as determined by Kissinger, Augis‐Bennett and Ozawa models. Fourier transform infrared (FTIR) and Raman spectroscopy analysis confirmed the structural modification with the gradual addition of Al₂O₃ in the glass matrix revealing dominant presence of AlO₄ tetrahedral units in 10AlG sample unlike in 5AlG sample which exhibited the manifestation of AlO₆ units. Such structural variation has further been substantiated from the estimated elastic properties like Young's modulus (E), shear modulus (G), bulk modulus (K), longitudinal modulus (L), and mean ultrasonic velocity (U_m) by showing a decrease for 5AlG sample in comparison with 0AlG sample followed by subsequent increase for 10AlG sample.     

High-temperature oxidation behaviour of vacuum hot-pressed WC-15 wt% Al2O3 composites

In this study, WC-15 wt% Al₂O₃ composites were prepared using the vacuum hot-pressing sintering method. The high-temperature (600–800 °C) oxidation behaviour of WC-15 wt% Al₂O₃ composites was investigated and compared with that of WC-6wt.%Co cemented carbides. The results showed that the oxidation resistance of WC-15 wt% Al₂O₃ composites was better than that of WC-6wt.%Co cemented carbides at relatively high temperatures (700–800 °C). At 800 °C, an oxide layer was formed on the surface of WC-15 wt% Al₂O₃ composites, which included WO₃ and Al₂O₃. The dispersion of alumina in the composites hindered the further diffusion of oxygen, thus improving the oxidation resistance. The Arrhenius activation energies of WC-15 wt% Al₂O₃ composites and WC-6wt.%Co cemented carbides were 110 ± 1 kJ/mol and 167 ± 2 kJ/mol at 600–800 °C, respectively.     

Influence of Parameters on Glycerol Hydrogenolysis over a Cu/Al2O3 Catalyst

The influence of technological parameters like hydrogen pressure, temperature, glycerol concentration in aqueous solution, amount of catalyst, stirring speed, and reaction time on glycerol hydrogenolysis to 1,2‐propanediol over a Cu/Al₂O₃ catalyst prepared by coprecipitation was investigated. Functions describing the process were glycerol conversion as well as selectivity to 1,2‐propanediol and to by‐products in the liquid and gas phase. The structure and properties of synthesized Cu/Al₂O₃ were characterized by X‐ray diffraction, energy dispersive X‐ray microanalysis, BET surface area, average pore volume, and pore diameter. Catalyst recycle studies were also performed.     

CaO–SiO2–Al2O3–Y2O3 glasses as model grain boundary phases for Si3N4 ceramics

The glasses with compositions derived from the eutectic composition [37.78 (Y₃Al₅O₁₂)·62.22 (SiO₂)] of the quasi-binary glass system (Y₃Al₅O₁₂)-(SiO₂) with addition of up to 20 mol.% CaO were investigated as model grain boundary phases for Si₃N₄ ceramics. The influence of CaO as model impurity on the physical properties of the glass (density, thermal expansion) and on the crystallisation behaviour was studied. Although the initial composition of the basic glass was that of yttrium-aluminium garnet (Y₃Al₅O₁₂–YAG), no crystalline YAG was detected. Apart from yttrium disilicate (Y₂Si₂O₇), anorthite (CaAl₂Si₂O₈), tricalcium aluminate (Ca₃Al₂O₆), and calcium yttrium oxide silicate (Ca₄Y₆O(SiO₄)₆), a new phase was detected, not found in the powder diffraction file (PDF) database. Cavities were formed within the devitrified glass due to the volume contraction after crystallisation. Possible implications for the mechanical properties of Si₃N₄ ceramics sintered with addition of Y₂O₃–Al₂O₃ are discussed in terms of the observed compositional dependences of the physical properties of CaO–Y₂O₃–Al₂O₃–SiO₂ glasses.     

Effect of Alumina Reactivity on the Densification and Properties of Al2O3–Cr2O3 Refractories

Alumina‐chrome (Al₂O₃–Cr₂O₃) refractories with Al₂O₃:Cr₂O₃ molar ratio 1:1 were synthesized in the temperature range of 1400–1700°C by conventional solid–oxide reaction route. The effect of different aluminas (viz., hydrated and calcined) on the densification, microstructure, and properties of Al₂O₃–Cr₂O₃ refractories was investigated without changing the Cr₂O₃ source. The starting materials were analyzed to determine the chemical composition, mineralogy, density, surface area, and particle size. Sintered materials were characterized in terms of densification, phase assemblage, and mechanical strength at room temperature and at higher temperatures. Microstructural evolution at different sintering temperature was correlated with sintering characteristics. It can be concluded that the Al₂O₃–Cr₂O₃ refractories prepared with hydrated alumina as Al₂O₃ source show better densification and hot mechanical strength than corresponding calcined variety.