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.     

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.     

Phase Formation in Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–ZrO<Subscript>2</Subscript>–CeO<Subscript>2</Subscript> Nanopowders Modified with Calcium Cations

We have studied phase formation in calcium-modified Al₂O₃–ZrO₂–CeO₂ nanopowders during sol–gel synthesis. The results demonstrate that heat treatment of the nanopowders first leads to the formation of a zirconium dioxide-based solid solution stabilized with cerium cations. Raising the heat treatment temperature helps the crystallization of corundum, a stable phase of aluminum oxide, to reach completion. In the temperature range 1400–1550°C, we observe the formation of a second aluminum-containing phase: calcium cerium hexaaluminate consisting of long prismatic grains.     

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.     

Influence of Bi substitution on microwave dielectric properties of BaO–La<Subscript>2</Subscript>O<Subscript>3</Subscript>–Sm<Subscript>2</Subscript>O<Subscript>3</Subscript>–TiO<Subscript>2</Subscript> ceramics

The influences of Bi substitution on microwave dielectric properties of Ba₄(La_0.5Sm_0.5)_9.33Ti₁₈O₅₄ solid solutions were investigated. Dielectric ceramics with general formula Ba₄(La_(0.5−z)Sm_0.5Bi _z )_9.33Ti₁₈O₅₄, z = 0.0–0.2 were prepared by conventional solid state route. The structural analysis of all the samples was carried out by X-ray diffraction and scanning electron microscopy. The dielectric properties were investigated as a function of Bi contents using open-ended coaxial probe method in the frequency range 0.3–3.0 GHz at room temperature. Dielectric constant varies from 83 to 88 and loss tangent from 2.1 × 10⁻³ to 5.5 × 10⁻³ at 3 GHz with temperature coefficient of resonant frequency changing from 106.7 to −8.4 ppm/oC as Bi contents increases from z = 0.00–0.20. It has been found that dielectric constant and temperature coefficient of resonant frequency improve whereas loss tangent is adversely affected with increase in Bi substitution.     

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.     

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%.     

Microhardness and fracture toughness of ZrO<Subscript>2</Subscript>–Sc<Subscript>2</Subscript>O<Subscript>3</Subscript> solid electrolyte,doped with rare-earth and transition metals

The influence of low concentrations (1 mol %) of co-dopants (Y, Ce, Gd, Er, La, Zn, Mn, Co and Cu) on the microhardness and fracture toughness of Zr_0.81Sc_0.19O_2–δ (10.5ScSZ) solid electrolyte was studied by the indentation method. It was shown that co-doping of 10.5ScSZ by the rare-earth elements (Y, Ce, Gd, Er) results in microhardness increase on 4–45% due to stabilization of cubic phase in the grains, while the microhardness changing upon transition metals (Mn, Cu, Co, Zn) introduction is caused by the grain boundaries modification. The microhardness decreases on ~4 and 10% upon doping by Mn and Cu, accordingly, whereas the introduction of Co and Zn results in its increase approximately by 2 times. It was shown also that the influence of all investigated dopants on the fracture toughness is insignificant. The maximal effect observed for Cu was the fracture toughness increase from 2.1 up to 2.6 MPa m^0.5.     

Preparation,structure and microwave dielectric properties of 3MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–3TiO<Subscript>2</Subscript> ceramics

3MgO–Al₂O₃–3TiO₂ (MAT) ceramics were prepared by a conventional solid-state reaction method. The crystal structure, sintering behavior and microwave dielectric properties of ceramics were investigated using X-ray diffraction, scanning electron microscopy and network analyzer. MAT ceramics contained the coexistence of three phases, including MgAl₂O₄, MgTiO₃ and MgTi₂O₅. The ceramics sintered at 1350 °C for 4 h presented excellent comprehensive performances with relative permittivity (ε _r ) of 15.4, quality factor (Q × f) of 91,000 GHz and temperature coefficient of resonant frequency (τ _f ) about ?55.1 ppm/°C.     

Frequency dependence of dielectric properties of CaO–SrO–Li<Subscript>2</Subscript>O–Ln<Subscript>2</Subscript>O<Subscript>3</Subscript>–TiO<Subscript>2</Subscript> ceramics

CaO–SrO–Li₂O–Ln₂O₃–TiO₂ ceramics were prepared by solid state reaction method, where Ln₂O₃ consists of equal proportions of Nd₂O₃ and Sm₂O₃. Dielectric properties and crystal structure were investigated with respect to the content of TiO₂. Single phase with an orthorhombic perovskites structure was formed within the composition range of investigation. The frequency dependence of dielectric properties of the present ceramics was extensively investigated. Dielectric constant was less sensitive to frequency. However, dielectric loss and temperature coefficients were both very sensitive to frequency and gradually decreased with increasing frequency, such as the variation was more than ten times between 1 MHz and several GHz. The relationship between the temperature coefficient and dielectric loss was also discussed at different frequencies. And the mechanism of the frequency dependence was discussed in term of the role of Li ions.     

Effect of the ZrO<Subscript>2</Subscript> concentration on the crystallization behavior and the mechanical properties of high-strength MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> glass–ceramics

High-strength, colorless glass–ceramics in the MgO/Al₂O₃/SiO₂ system with high concentrations of ZrO₂ and a great potential for technical application, e.g., as high-performance hard disc substrates, are investigated. ZrO₂ concentrations from 6 to 9 mol% are added to a stoichiometric cordierite glass to investigate the influence of the concentration of the nucleating agent on the crystallization behavior and the mechanical properties. The phase formation and the microstructure of the glass–ceramics are studied using X-ray diffraction and scanning electron microscopy including electron backscatter diffraction. It is shown that the volume crystallization of ZrO₂, a low-/high-quartz solid solution (low-/high-QSS), and spinel is accompanied by the surface crystallization of indialite. This phase offers a much smaller coefficient of thermal expansion than the other crystal phases, which may induce high compressive stresses in the surface layer of the glass–ceramics after cooling and seems to result in excellent mechanical properties of the material. Biaxial flexural strengths of up to 1 GPa were measured. Higher ZrO₂ concentrations reduce the surface crystallization of indialite and decrease the mean size of the crystals resulting in a higher translucency. The volume-crystallizing phases and the mechanical properties of the glass–ceramics do not seem to be significantly affected by the analyzed ZrO₂ concentrations.     

Characterization and analysis of CaO–SiO<Subscript>2</Subscript>–B<Subscript>2</Subscript>O<Subscript>3</Subscript> ternary system ceramics

The dielectric, thermal and mechanical properties of CaO–SiO₂–B₂O₃ ternary system ceramics by solid-phase method have been carried out and quantitive analysis been examined by X-ray diffraction (XRD) patterns. The results showed that the major crystalline phase of CaO–SiO₂–B₂O₃ ternary system ceramics was wollastonite (about 90 wt%) which existed at the temperature ranging from 950 to 1,100 °C. It is also observed that wollastonite could be transformed to pseudowollastonite at 1,200 °C. In addition, with increase in calcination temperature, the amount of wollastonite increases. When the sintering temperature is at 1,100 °C, the amount of wollastonite has a maximum value of 92.7 wt%. Accordingly, CaO–SiO₂–B₂O₃ ternary system ceramics achieved excellent properties at 1,100 °C, such as dielectric constant of 8.38, dielectric loss of 1.51 × 10⁻³ at 1 MHz, linear thermal-expansion coefficient (300 K) of 6.68 × 10⁻⁶/K, bending strength of 121.75 Mpa. Analysis of the mechanical and dielectric properties showed that the measured bending strength, dielectric constant and loss of CaO–SiO₂–B₂O₃ ternary system ceramics can be substantially modified and improved by controlling the sintering temperature, in particular due to the amount of wollastonite crystalline phase and size of grains.     

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.     

Syntheses and proton conductivity of mesoporous Nd<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> and NdOCl–SiO<Subscript>2</Subscript> composites

Two mesoporous oxide composites of Nd₂O₃–SiO₂ and NdOCl–SiO₂ were synthesized using SBA-15 as a template and neodymium nitrate or neodymium chloride as a precursor. The porous Nd₂O₃–SiO₂ with a SBA-15-like structure has amorphous walls and the porous NdOCl–SiO₂ with a replicated structure of SBA-15 has crystalline walls. These porous materials were characterized by X-ray diffraction, transmission electron microscopy and nitrogen adsorption/desorption. They exhibited significant proton conductivities in the presence of moisture at low temperatures and the highest conductivity observed was 4.55 × 10⁻⁴ S/cm at 47 °C in wet air (RH = 28.6%).     

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.     

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.     

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.     

Electrical properties of R<Subscript>2</Subscript>O–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> glass–ceramics for anodic bonding

Temperature and frequency dependence on electrical properties (dielectric constant, dielectric loss and conductivity) of Li₂O–Na₂O–K₂O–Al₂O₃–SiO₂(R₂O–Al₂O₃–SiO₂) system glass–ceramics used as anodic bonding materials were discussed. The results showed that the main crystal phase of glass–ceramics was lithium metasilicate (Li₂SiO₃). Compared with the parent glass, both the dielectric constant and dielectric loss of glass–ceramics decreased, the dielectric constant and dielectric loss increased gradually with the increasing of the test temperature from room temperature to 400 °C, Testing frequency (30–300 MHz) had very little influence on the dielectric properties of samples. The electrical conductivity of glass–ceramics showed a trend of first decrease and then increase with the increasing of temperature. The glass–ceramics which has a lower dielectric constant, dielectric loss and better stability under high frequency was obtained after an appropriate heat treatment; it could be used as anodic bonding materials under very high frequency.     

Thermodynamic properties of Er<Subscript>2</Subscript>O<Subscript>3</Subscript> · 2ZrO<Subscript>2</Subscript> in the range 6–1400 K

The isobaric heat capacity of the Er₂O₃ · 2ZrO₂ solid solution has been determined by adiabatic calorimetry and differential scanning calorimetry, and the enthalpy increment, entropy, and reduced Gibbs energy change of the solid solution have been calculated in the temperature range 6–1400 K with no allowance for the low-temperature (<6 K) magnetic transformations.