Catalytic combustion of methane over Pt and PdO-supported CeO<Subscript>2</Subscript>–ZrO<Subscript>2</Subscript>–Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts

Catalytic combustion of methane was investigated on Pt and PdO-supported CeO₂–ZrO₂–Bi₂O₃/γ-Al₂O₃ catalysts prepared by a wet impregnation method in the presence of polyvinylpyrrolidone. The catalysts were characterized by X-ray fluorescence analysis, X-ray powder diffraction, X-ray photoelectron spectra, transmission electron microscopy, and BET specific surface area measurements. The Pt/CeO₂–ZrO₂–Bi₂O₃/γ-Al₂O₃ and PdO/CeO₂–ZrO₂–Bi₂O₃/γ-Al₂O₃ catalysts were selective for the total oxidation of methane into carbon dioxide and steam, and no by-products such as HCHO, CO, and H₂ were obtained. The catalytic activities of the PdO/CeO₂–ZrO₂–Bi₂O₃/γ-Al₂O₃ catalysts were relatively higher than those of the Pt-supported catalysts, due to the facile re-oxidation of metallic Pd into PdO based on lattice oxygen supplied from the CeO₂–ZrO₂–Bi₂O₃ bulk. A decrease in the calcination temperature during the preparation process was found to be effective in enhancing the specific surface area of the catalysts, whereby particle agglomeration was inhibited. Optimization of the PdO amount and calcination temperature enabled complete oxidation of methane at temperatures as low as 320 °C on the 11.6 wt% PdO/CeO₂–ZrO₂–Bi₂O₃/γ-Al₂O₃ catalyst prepared at 400 °C.     

Vaporization in the Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–MgO system

The pseudobinary system Al₂O₃–MgO has been studied in the temperature range 1750–2100 K by the Knudsen effusion method in combination with mass spectrometric analysis of the vapor phase. Over the entire composition range, except for the 100 mol % Al₂O₃ boundary, the vapor phase over the system consists of three species: Mg, O₂, and O. The partial pressures obtained have been used to construct a p–x section through the Al₂O₃–MgO phase diagram at 1900 K. The standard enthalpy of formation of the MgAl₂O₄ spinel at 298 K has been determined by third-law calculations:–2301.61 ± 11.00 kJ/mol. We have derived equations for the temperature dependences of the partial pressures of the vapor species over the Al₂O₃–MgO system.     

The crystallographic orientation relationship between Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> in the composite material Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/Al–Mg–Si alloy

The formation mechanism of spinels on Al₂O₃ particles in the Al₂O₃/Al–1.0 mass% Mg₂Si alloy composite material has been investigated by transmission electron microscopy (TEM) in order to determine the crystallographic orientation relationship. A thin sample of the Al₂O₃/Al–Mg–Si alloy composite material was obtained by the FIB method, and the orientation relationship between Al₂O₃ and MgAl₂O₄, which was formed on the surface of Al₂O₃ particles, was discovered by the TEM technique as follows:

Microstructure,interfaces and creep behaviour of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–Sm<Subscript>2</Subscript>O<Subscript>3</Subscript> (ZrO<Subscript>2</Subscript>) eutectic ceramic composites

New compositions in the melt-grown eutectic ceramics field are investigated for thermomechanical applications. This paper is focused on the Al₂O₃–Sm₂O₃–(ZrO₂) system. The studied compositions give rise to interconnected microstructures without anisotropy along the growth direction. At variance with the binary eutectic Al₂O₃–SmAlO₃, the homogeneity of the microstructure of the Al₂O₃–SmAlO₃–ZrO₂ ternary eutectic is less sensitive to the growth rate. Interfaces between the alumina and perovskite phases are investigated by high-resolution transmission electron microscopy (TEM). They are semi-coherent. In stepped interfaces, the facets are parallel to dense planes of each phase. The steps have a dislocation character and may accommodate both misfits. The ternary eutectic displays a very good creep behaviour with strain rates very close to those obtained on other previously studied eutectics in the Al₂O₃–RE₂O₃(RE = Y, Gd, Er)–ZrO₂ systems. The deformation micromechanisms are analysed by TEM in the three eutectic phases. After creep, dislocations are present in every phase. The activation of unusual slip systems (pyramidal slip in the alumina phase) shows that high local stresses can be reached. The presence of dislocation networks with low energy configurations is consistent with predominance of dislocation climb processes controlled by bulk diffusion.     

Synthesis and characterization of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–ZrO<Subscript>2</Subscript> nanocomposite powder by sucrose process

Nanocrystalline alumina–zirconia powders were prepared by a modified chemical route using sucrose, polyvinyl alcohol (PVA) and metal nitrates followed by a post calcination process. The process involved dehydration of Al³⁺–Zr⁴⁺ ions-sucrose–PVA solution to a highly viscous liquid which on decomposition process produced a black precursor material. The obtained precursor were then calcined at various temperatures: 1,050, 1,100, 1,150, 1,200 and 1,250 °C for different soaking times (1, 2, 4 h) in air. The formation of a nanocomposite composed of α-alumina (~20 nm) and tetragonal (t) zirconia (~19 nm) crystallites were confirmed for the sample calcined at 1,200 °C for 2 h, based on our XRD and TEM results. However, for the samples calcined below 1,150 °C the composite formed were composed of metastable alumina (γ, δ, θ) as well as t-zirconia phases. Interestingly, the zirconia phase retained its tetragonal structure for all the samples calcined above 1,050 °C. This is possibly related to the “size effect” and reduction of surface enthalpy of the zirconia crystallites surrounded by Al³⁺ cations.     

Sintering and microstructure of materials based on the fluorohydroxyapatite–ZrO<Subscript>2</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> system

We have studied the influence of the sintering temperature and modifying additives on the phase composition, microstructure, and mechanical strength of a fluorohydroxyapatite-based composite ceramic material containing 20 wt % zirconia. The addition of 5 wt % alumina has been shown to prevent recrystallization processes and contribute to phase composition stabilization. Moreover, the addition of a sintering aid (2 wt %) has made it possible to lower the sintering temperature to 1200°C and raise the bending strength of the material to 143 MPa.     

Synthesis and properties of nanocrystalline 90 wt % ZrO<Subscript>2</Subscript>〈Y<Subscript>2</Subscript>O<Subscript>3</Subscript>, CeO<Subscript>2</Subscript>〉-10 wt % Al<Subscript>2</Subscript>O<Subscript>3</Subscript> powder

Using hydrothermal treatment of coprecipitated hydroxides, we have prepared nanocrystalline ZrO₂-rich ZrO₂-Y₂O₃-CeO₂-Al₂O₃ powder. The effect of heat treatment on the properties of the powder has been studied in the temperature range 400–1300°C. The powder has been shown to have a metastable phase composition, which is attributable to structural and size factors and also to the fact that the ZrO₂ and Al₂O₃ crystallites inhibit the growth of each other. Sintering the powder under various conditions, we have obtained ceramics with fracture toughnesses from 6.4 to 16.8 MPa m^1/2.     

Thermodynamic properties of Dy<Subscript>2</Subscript>O<Subscript>3</Subscript> · 2ZrO<Subscript>2</Subscript> and Ho<Subscript>2</Subscript>O<Subscript>3</Subscript> · 2ZrO<Subscript>2</Subscript> in the range 10–340 K

The low-temperature heat capacity of Dy₂O₃ · 2ZrO₂ and Ho₂O₃ · 2ZrO₂ has been determined by adiabatic calorimetry in the temperature range 10–340 K. The results have been used to calculate the entropy, enthalpy increment, and reduced Gibbs energy of the zirconates without taking into account their low-temperature magnetic transformations.     

Nanostructured Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–ZrO<Subscript>2</Subscript> composite synthesized by sol–gel technique: powder processing and microstructure

Al₂O₃–ZrO₂ composite gel powder was prepared by sol–gel route. The gel precursor compositions were preferred to achieve yield of 5–15 mol% zirconia after calcination of respective powders. The precursor gel was characterized by Differential Thermal Analysis (DTA)/Thermo Gravimetric (TG), IR and X-ray Diffraction study (XRD). The analysis reveal the gel contained pseudoboehmite and amorphous Zr(OH)₄, which was decomposed in three and two stages respectively. The phase transformation of alumina during calcination followed the sequence of pseudoboehmite → bayerite → boehmite → γ-Al₂O₃ → θ-Al₂O₃ → α-Al₂O₃, while that of ZrO₂ follows amorphous ZrO₂ → t-ZrO₂ → (t + m) ZrO₂. Fourier Transform Infrared Spectroscopy (FTIR) studies showed that the number of M–OH and M–O bond increases with zirconia due to a change in the cationic charge of the composite powder. Transmission Electron Microscopy (TEM) photograph of calcined powder exhibited the presence of dispersed as well as agglomerated nano sized spherical particles. SEM and Electron Probe Microscope Analysis (EPMA) confirmed the near uniform distribution of zirconia particles in the alumina matrix.     

Fabrication of Yb<Subscript>2</Subscript>O<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript>–SiO<Subscript>2</Subscript> Optical Fibers with a Perfect Step-Index Profile by the MCVD Process

An all-vapor phase MCVD process has been proposed for the fabrication of fiber preforms with a Yb₂O₃–Al₂O₃–P₂O₅–SiO₂ multicomponent glass core. We have investigated the tubular preform collapse into a rod and demonstrated approaches capable of preventing P₂O₅ losses in the central part of the core during the collapse process. Preforms with a flat, perfect step-index profile have been fabricated.     

Crystallization and microstructural evolution of MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>–TiO<Subscript>2</Subscript>–La<Subscript>2</Subscript>O<Subscript>3</Subscript> glass-ceramics

Crystallization and microstructure of glasses with the molar compositions 1MgO·1.2Al₂O₃·2.8SiO₂·1.2TiO₂·xLa₂O₃ (x = 0.1 and 0.4) were thermally treated at different temperatures in the range from 950 to 1250 °C and then analyzed by X-ray diffraction and scanning electron microscopy, in combination with energy-dispersive X-ray spectroscopy and electron backscatter diffraction. It was found that the microstructure is first homogeneous with the precipitation of randomly distributed crystals and then indialite domains with embedded perrierite and rutile crystals are formed. For higher temperatures or prolonged times, more domains appear and expand into the bulk of the sample. Finally, the entire sample consists of the indialite domains and the boundaries that are enriched in rutile, perrierite, and magnesium aluminotitanate. Nevertheless, very distinct differences are observed between the samples with different La₂O₃ concentrations. For the sample with x = 0.4, the domains were detected at lower temperatures, while the quantity and size of the domains increase faster due to the promoted precipitation of indialite. For the sample with x = 0.1, in addition to the domain boundaries, secondary boundaries between the “regions” (assemblages of the domains) are observed in a larger length scale. The average size of the crystalline phases found between the “regions” is larger than that typically observed at the domain boundaries. The sizes of the crystals at the boundaries decrease with higher concentrations of La₂O₃, and the crystals (especially perrierite) within the domains become larger, resulting in a more homogeneous microstructure. This results in better dielectric properties, i.e., much higher quality factor for the sample with x = 0.4 in comparison to that with x = 0.1 after heat-treatment at 1150 or 1250 °C.     

Characterization of microstructure and properties of Al–Al<Subscript>3</Subscript>Zr–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> composite

Aluminium-based metal matrix composite strengthened by in situ Al₂O₃ and Al₃Zr particles were synthesized by powder metallurgy route. Phase analysis by X-ray diffraction and scanning electron microscopy revealed that the reaction between Al and ZrO₂ produced Al₂O₃ and Al₃Zr phases in the sintered composites. The hardness of the composite is a strong function of sintering temperature as well as the volume fraction of reinforcements. The dry sliding wear test results clearly indicated that increasing the volume fraction of zirconia particles in the composite improved the wear resistance. Microcutting, ploughing, delamination and oxidation were the main mechanisms of wear.     

Spectroscopic characterisation of local structure in Y<Subscript>2</Subscript>O<Subscript>3</Subscript>–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> glasses doped with gadolinium

Gadolinium doped bismuth borate glasses containing up to 30 mol% Y₂O₃ were prepared by fast melt quenching method. The effect of yttrium on the local order in 3B₂O₃ · Bi₂O₃ and B₂O₃ · Bi₂O₃ glass matrices, particularly on the bismuth sites, was investigated by infrared (IR) spectroscopy and electron paramagnetic resonance (EPR) of Gd³⁺ ions. The IR results show that the local structure is more ordered in the glass system with higher bismuth content and the progressive addition of yttrium increases the local disorder in both bismuth–borate glass matrices. The EPR results indicate that Gd³⁺ ions occupy both bismuth and yttrium sites and reflect the same structural disorder like that suggested by IR results.     

Vacuum arc deposition of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–ZrO<Subscript>2</Subscript> coatings: arc behavior and coating characteristics

Al₂O₃–ZrO₂ coatings were deposited using a vacuum arc deposition system equipped with two co-planar cathodes. The plasma was injected into a cylindrical magnetic duct through annular anode apertures toward a substrate or an electrostatic ion current probe positioned on the duct axis, in vacuum and in a low-pressure oxygen or argon + oxygen background. Ion current and arc voltage measurements and visual observation of the cathode spots were used to find stable arcing conditions, using a straight plasma duct configuration. The cathode spot operation and transport of the plasma beam in the duct were studied as a function of arc current (I _arc = 25–200 A) and oxygen or oxygen + argon pressures (P = 0.1–1.5 Pa). Coatings were fabricated by exposing Si or WC–Co substrates simultaneously to Al and Zr plasmas using a 1/8 torus filter configuration in O₂ + Ar pressures. The coating composition, structure, microhardness, adhesion, and wear behavior were studied as functions of the deposition parameters. Favorable conditions for stable arcing were obtained with I _arc = 75 and 100 A for Al and Zr plasmas, respectively. The ion current decreased, and the arc voltage increased with the oxygen pressure. Behavior of the ion current and arc voltage suggested that cathode poisoning started at P = 0.5 Pa. Deposition rates were 0.3-0.6 μm/min, depending on the substrate position. All coatings were “Zr rich”, i.e., the Zr:Al ratio was in the range of 1.2–5.6 depending on the substrate position and deposition conditions. The coatings with higher ZrO₂ concentration were harder and had better resistance to wear. The coating’s hardness reached a maximum of ~22–24 GPa at a deposition temperature of 500 °C or a negative bias voltage of 75–100 V.     

In vitro dissolution behavior of SiO<Subscript>2</Subscript>–MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–K<Subscript>2</Subscript>O–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–F glass–ceramic system

Herein, we report the results of the in vitro dissolution tests, which were carried out by immersing the selected glass-ceramic samples in artificial saliva (AS) for various time periods of up to 42 days. In our experiments, the SiO(2)-MgO-Al(2)O(3)-K(2)O-B(2)O(3)-F glass ceramics with different crystal morphology and crystal content were used and a comparison is also made with the baseline glass samples (without any crystals). The bioactivity of the samples was probed by measuring the changes in pH, ionic conductivity and ionic concentration of AS following in vitro dissolution experiments. High resistance of the selected glass-ceramic samples against in vitro leaching has been demonstrated by minimal weight loss (<1%) and insignificant density change, even after 6 weeks of dissolution in artificial saliva. While XRD analysis reveals the change in surface texture of the crystalline phase, FT-IR analysis weakly indicated the Ca-P compound formation on the leached surface. The experimental measurements further indicate that the leaching of F(-), Mg(2+) ions from the sample surface commonly causes the change in the surface chemistry. Furthermore, the presence of (Ca, P, O)-rich mineralized deposits on the leached glass-ceramic surface as well as the decrease in Ca(2+) ion concentrations in the leaching solutions (compared to that in the initial AS solution) provide evidences of the moderate bioactive or mild biomineralisation behaviour of investigated glass-ceramics.     

Formation and Acid–Base Surface Properties of Highly Dispersed η-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Nanopowders

Highly dispersed η-Al₂O₃-based nanopowders have been prepared via glycine–nitrate combustion followed by heat treatment in air. The resultant materials have been characterized by X-ray diffraction, Fourier transform IR spectroscopy, scanning electron microscopy, simultaneous thermal analysis, and other techniques. We have optimized the glycine-to-nitrate ratio (G/N = 0.2) and found heat treatment conditions for combustion products (isothermal holding at a temperature of 700°C for 6 h) that allow one to obtain single- phase nanocrystalline η-Al₂O₃ powders with an average particle size of 5 ± 1 nm and specific surface area of 54 ± 5 m²/g. The acid–base surface properties of the η-Al₂O₃ nanopowder have been analyzed using pyridine sorption–desorption processes as an example. The specific concentrations of weak, intermediate, and strong Lewis acid centers on the surface of the η-Al₂O₃ nanocrystals have been shown to markedly exceed those on the surface of commercially available γ-Al₂O₃ (A-64). The synthesized nanopowders can thus be used as effective supports of acid catalysts.     

Synthesis of Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Ce<Superscript>3+</Superscript> phosphor in the Y<Subscript>2</Subscript>O<Subscript>3</Subscript>–Al metal–CeO<Subscript>2</Subscript> ternary system

Garnet phosphor Y₃Al₅O₁₂:Ce³⁺ is prepared in the Y₂O₃–Al metal–CeO₂ ternary system by the solid-state reaction method in the air. For the first time, metal Al is used as a source of aluminum for the reaction instead of traditional oxide Al₂O₃. It is shown that the chemical reaction can be realized at lower temperatures and without use of special reducing atmosphere. The structural and spectroscopic properties of the prepared powder phosphor are very close to those earlier reported for the Y₃Al₅O₁₂:Ce³⁺ single crystal.     

Effect of heat treatment on the properties of nanocrystalline 80 wt % Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-20 wt % ZrO<Subscript>2</Subscript>〈CeO<Subscript>2</Subscript>, Y<Subscript>2</Subscript>O<Subscript>3</Subscript>〉 powder

We have studied the evolution of nanocrystalline 80 wt % Al₂O₃-20 wt % ZrO₂〈CeO₂, Y₂O₃〉 powder prepared through hydroxide coprecipitation followed by hydrothermal decomposition of the hydroxides and firing at temperatures from 400 to 1300°C. α-Al₂O₃ has been shown to form at 850°C. The metastable phase F-ZrO₂ persists up to this temperature. The variation in the morphology of the powder is topologically continuous. The processes induced by heat treatment of the nanocrystalline powder are interpreted in terms of the evolution of an open system.     

Phase relations in the Cu<Subscript>2</Subscript>Te–Al<Subscript>2</Subscript>Te<Subscript>3</Subscript> semiconductor system

The T-x phase diagram of the Cu₂Te–Al₂Te₃ semiconductor system was achieved experimentally using 24 different mixtures of the binary compounds. The results of X-ray powder diffraction, differential thermal analysis, and electron microprobe analysis are presented. It was established that only one ternary compound CuAlTe₂ exists in this system crystallizing in the tetragonal structure of chalcopyrite with lattice constants at room temperature a = 6.035(5) and c = 11.94(1) Å. The maximal homogeneity region of this compound was discovered being limited by compositions with 0.474 and 0.544 molar part of Al₂Te₃ at 673 K. CuAlTe₂ decomposes peritectically at 1,183 K to (Cu₂Te)_0.97(Al₂Te₃)_0.03 alloy with the structure of Cu₂Te and liquid with the composition close to (Cu₂Te)_0.40(Al₂Te₃)_0.60 which transforms into homogeneous liquid region at 1,240 K.     

The influence of high-temperature sintering on microstructure and mechanical properties of free-standing APS CeO<Subscript>2</Subscript>–Y<Subscript>2</Subscript>O<Subscript>3</Subscript>–ZrO<Subscript>2</Subscript> coatings

In this study, ceria–yttria co-stabilized zirconia (CYSZ) free-standing coatings, deposited by air plasma spraying (APS), were isothermally annealed at 1315 °C in order to explore the effect of sintering on the microstructure and the mechanical properties (i.e., hardness and Young’s modulus). To this aim, coating microstructure, before and after heat treatment, was analyzed using scanning electron microscopy, and image analysis was carried out in order to estimate porosity fraction. Moreover, Vickers microindentation and depth-sensing nanoindentation tests were performed in order to study the evolution of hardness and Young’s modulus as a function of annealing time. The results showed that thermal aging of CYSZ coatings leads to noticeable microstructural modifications. Indeed, the healing of finer pores, interlamellar, and intralamellar microcracks was observed. In particular, the porosity fraction decreased from ~10 to ~5% after 50 h at 1315 °C. However, the X-ray diffraction analyses revealed that high phase stability was achieved, as no phase decomposition occurred after thermal aging. In turn, both the hardness and Young’s modulus increased, in particular, the increase in stiffness (with respect to “as produced” samples) was equal to ~25%, whereas the hardness increased to up to ~60%.