Heteroepitaxial ZnO/sapphire (0 0 0 1) structure prepared by sol–gel process

ZnO thin films were grown on sapphire (0 0 0 1) substrates by sol–gel process and their structural and optical properties were characterized in detail. High-quality texture was obtained by using precursor solution of zinc acetate and ethanolamine in 2-methoxyethanol, pyrolyzed at 300 °C, then heated at 500 °C, and finally annealed at 750 °C. Highly c-axis oriented ZnO films were confirmed by X-ray θ–2θ scan. A relatively high transmittance in the visible spectra range and clear absorption edge of the film were observed. Epitaxial relationship between ZnO and sapphire and photoluminescence of the film were examined by using a X-ray pole-figure analysis and He–Cd laser. Near-band-edge emission with a deep-level emission was observed.     

High temperature oxidation behavior of porous MoAlB ceramic from 800 °C to 1100 °C in air

MoAlB possesses the characteristics of both metals and ceramic materials, which has attracted extensive attention due to its excellent high-temperature oxidation resistance. For this reason, porous MoAlB is considered applicable to the practice of filtration under harsh environment. In this study, the high-temperature oxidation behavior of porous MoAlB ceramics is systematically studied at the temperatures ranging from 800 to 1100 °C. According to the results, the porous MoAlB exhibits good oxidation resistance at a maximum temperature of 1000 °C. The oxidation kinetics of porous MoAlB can be divided into three stages, and the estimated activation energies of the three stages are 253.83 kJ·mol⁻¹, 367.48 kJ·mol⁻¹ and 317.84 kJ·mol⁻¹, respectively. In the stable stage at 1000 °C, the quadratic mass gain per unit area shows linearity over time, and the oxidation rate of porous MoAlB reaches 37.31 mg²·cm⁻⁴·h⁻¹. As revealed by the analysis of the composition and microstructure of oxide layers, the main components of the oxide layer include MoO₃, MoO₂, Al₂O₃, B₂O₃. With the extension of oxidation time, the content of Al₂O₃ in the oxide films increases. The average pore size, permeability and open pore porosity of porous MoAlB show a trend of first decreasing and then tending to be stable. In addition, a discussion is conducted on the high-temperature oxidation mechanism of porous MoAlB.     

Liquid–Liquid Equilibria of Ternary Systemscis-1,2-Dimethylcyclohexane + Toluene + Sulfolane

Liquid–Liquid Equilibrium (LLE) data for three Ternary Systems comprising cis-1,2-dimethylcyclohexane + toluene + sulfolane were measured at 298.15, 313.15 and 328.15 K under atmospheric pressure. The phase diagrams for the ternary systems were presented. The reliability of the experiment data was tested using the Othmer–Tobias correlation. The LLE data were then correlated with the universal functional activity coefficient for liquid–liquid systems (UNIF-LL) and non-random two liquid using dataset 2 (NRTL/2) activity coefficient models to obtain the binary interaction parameters as programmed by the Aspen Plus simulation. The results showed that the experimental data were satisfactorily represented by both the UNIF-LL and the NRTL/2 models as revealed from the very small values of the root mean square error and the absolute deviation in composition.     

Demixing pressures of hydroxy-terminated poly(dimethylsiloxane)–carbon dioxide binary mixtures at 313.2 K, 323.2 K and 333.2 K

The phase behavior of PDMS(OH)–CO₂ binary mixtures was investigated. Two different molecular weight PDMS(OH) were utilized and the demixing pressures were determined at three temperatures for a wide composition range. Both of these polymers were found to form miscible mixtures with CO₂ at all compositions at pressures lower than 31 MPa in the temperature range 313.2–333.2 K. Depending on the composition of the binary mixtures, two types of phase separation was observed during depressurization; the bubble point and the cloud point. In addition, at specific weight fractions a color change was also observed which was attributed to the mixture critical point. The demixing pressures were observed to increase with temperature and decrease with increasing polymer weight fraction. In addition, higher demixing pressures were obtained for the higher molecular weight polymer mixtures. The bubble point data were modeled by using Sanchez–Lacombe equation of state (SLEoS) and the binary interaction parameters were regressed at the studied temperatures. It was observed that the binary interaction parameters decreased with increasing temperature.     

Heterogeneous oxidation of 2-octanol on 5 wt%Pt–1 wt%Bi/Carbon catalyst

The low activity of 5%Pt–1%Bi/Carbon for the oxidation of 2-octanol at atmospheric pressure and 343 K was investigated. Using solvents such as heptane and p-xylene, it was shown that the reaction rates decrease dramatically shortly after the start of the reaction due to poisoning by product adsorption. Hence this work investigates the effect of using different solvent mixtures on the oxidation reaction of 2-octanol with 5%Pt–1%Bi/Carbon. Mixtures with different volumetric ratios of heptane and dioxane were investigated to find the best composition capable of effectively removing the adsorbed amphiphilic ketone. It is apparent that the reaction rate is correlated with the adsorption coefficient of ketone on the catalyst, such that the maximum reaction rate occurs at the lowest ketone adsorption coefficient, corresponding to a concentration of 16–18%v/v dioxane. A model based on a Langmuir–Hinshelwood mechanism has been successfully fitted to the experimental rates.     

Size distribution of exhaled particles in the range from 0.01 to 2.0 μm

This study investigates the number size distribution of endogenously produced exhaled particles during tidal breathing and breathing with airway closure. This is the first time that the region below 0.4 μm has been investigated. The particle concentration was generally lower for tidal breathing than for airway closure, although the inter-individual variation was large. During tidal breathing, the size distribution peaks at around 0.07 μm. This peak is still present during the airway closure manoeuvre, but an additional broad and strong peak is found between 0.2 and 0.5 μm. This suggests that different mechanisms govern the generation of particles in the two cases. The particles produced from airway closure may be attributed to formation of film droplets in the distal bronchioles during inhalation. It is speculated that the very small particles are film droplets originating from the alveolar region.     

Phase relations in silicon and germanium nitrides up to 98 GPa and 2400°C

Phase relations in silicon and germanium nitrides (Si₃N₄ and Ge₃N₄) were investigated using a Kawai-type multianvil apparatus and a laser-heated diamond anvil cell combined with a synchrotron radiation. The pressure-induced phase transition from the β to γ (cubic spinel-type structure) phase was observed in both compositions. We observed the coexistence of the β and γ phases in Si₃N₄ at 12.4 GPa and 1800°C, while the appearance of single phase γ-Ge₃N₄ was observed at pressures above 10 GPa. Our observations under higher pressures revealed that γ-Si₃N₄ and γ-Ge₃N₄ have wide stability fields and no postspinel transition was observed up to 98 GPa and 2400°C in both compositions. Using the room-temperature compression curves of these materials, the bulk moduli (K₀) and their pressure derivatives (K′₀) were determined: K₀ = 317 (16) GPa and K′₀ = 6.0 (8) for γ-Si₃N₄; K₀ = 254 (13) GPa and K′₀ = 6.0 (7) for γ-Ge₃N₄.     

Crystal structure,mixture behavior,and microwave dielectric properties of novel temperature stable (1 − x)MgMoO4 − xTiO2 composite ceramics

Novel temperature stable MgMoO₄–TiO₂ microwave dielectric ceramics were prepared by a solid state reaction process at low temperature (950 °C). As TiO₂ content increases, the relative permittivity increases while the Q × f value decreases, and the variation mechanisms are proposed, respectively. The temperature coefficient of resonant frequency (τ_f) shifts to the positive direction as TiO₂ is added. The mixture mechanisms of τ_f value for two-phase composite materials are supposed. A near-zero τ_f value (3.2 ppm/°C) is obtained when x = 0.3, with ε_r = 9.13 ± 0.03 and Q × f = 11,990 GHz. The 0.7MgMoO₄–0.3TiO₂ composites are considered to be appropriate as a low temperature co-fired ceramic material for microwave wireless communication applications.     

Phase evolution and chemical durability of Zr1-xNd xO2-x/2 (0 ≤ x ≤ 1) ceramics

A series of Zr_1-xNd _xO_2-x/2 (0 ≤ x ≤ 1) ceramics was prepared by solid-state reaction method. The effects of Nd content on the phase evolution were investigated. The chemical durability of resulting waste forms was also examined. The results show that the ceramics with x < 0.1 show monoclinic and cubic zirconia phase, with 0.2 ≤ x < 0.4 exhibit a single cubic phase, with 0.4 ≤ x ≤ 0.6 exhibit a single pyrochlore phase, with 0.6 < x < 0.8 exhibit a single cubic phase and remain cubic phases and hexagonal Nd₂O₃ when 0.8 ≤ x ≤ 1. The unit cell parameters of the Nd-doped zirconia samples increase as the Nd content increases. Moreover, the normalized element release rates of Nd element in Nd-doped zirconia ceramics firstly decrease with leaching time and almost no change after 21 days (∼0⁻⁶ g m⁻² d⁻¹), demonstrating its good chemical durability.     

Oxyacetylene ablation of (Hf0.2Ti0.2Zr0.2Ta0.2Nb0.2)C at 1350 − 2050 °C

Ablation resistance of a multi-component carbide (Hf_0.2Ti_0.2Zr_0.2Ta_0.2Nb_0.2)C (HTZTNC) was investigated using an oxyacetylene flame apparatus. When the surface temperature of the HTZTNC was below 1800 °C, (Nb, Ta)₂O₅, (Hf, Zr)TiO₄, and (Hf, Zr)O₂ were found to be the main oxidation products, while at higher temperature, formation of (Hf, Zr, Ti, Ta, Nb)O_x was favored and its content gradually increased with the increase in ablation temperature. Based on the ablation results and thermodynamic simulation analysis, a possible ablation mechanism of HTZTNC was proposed. Active oxidation of TiC and outward diffusion of TiO were demonstrated to occur during the ablation process, which constitute the critical steps for the ablation of HTZTNC. These results can contribute to the design of ablation resistant ultra-high-temperature ceramics.     

Microporous solid based solely upon an intermolecular NH ⋯ O and NH ⋯ Cl hydrogen bond network

A novel porous solid of ruthenium(II, III) dimer complex, [Ru₂(p-O₂CC₆H₄NHCO^tBu)₄Cl], constructed by intermolecularly linking the hydrogen bonds of NH ⋯ O and NH ⋯ Cl was synthesized and the porous structure was crystallographically determined. The dried crystalline solid shows a high BET surface area determined by measuring the adsorption of nitrogen gas and water vapor.     

Frequency and temperature dependent electrical properties of Ni0.7Zn0.3CrxFe2−xO4 (0 ≤ x ≤ 0.5)

Series of the ferrite samples with a chemical formula Ni_0.7Zn_0.3Cr_xFe_2?xO₄ (x = 0.0–0.5) were prepared by a sol–gel auto-combustion method and annealed at 600 °C for 4 h. The prepared samples have the cubic spinel structure with no impurity phase. As the Cr³⁺ content x increases, the unit cell dimensions decrease with an increase in Cr³⁺ content x. The crystallite size is decreases from 37 nm to 21 nm as the Cr³⁺ content increases from x = 0.0 to 0.5. Resistivity increases whereas dielectric constant decreases with an increase in Cr³⁺ content x. Maxima in the dielectric loss tangent versus frequency appear when the frequency of the hopping charge carriers coincides with the frequency of the applied alternating field. Dielectric constant and dielectric loss tangent increases with increase in temperature. Saturation magnetization of sintered samples showed higher values as compared to as-prepared sample. Curie temperature deduced from AC susceptibility data decreases with increasing x.     

Synthesis and negative thermal expansion properties of solid solutions Yb2−xLaxW3O12 (0 ≤ x ≤ 2)

A new series of rare earth solid solutions Yb_2?xLa_xW₃O₁₂ were successfully synthesized by the solid-state method. Effects of substituted ion lanthanum on the microstructures and thermal expansion properties in the resulting Yb_2?xLa_xW₃O₁₂ ceramics were investigated by X-ray diffraction (XRD), thermogravimetric analyzer (TGA), field emission scanning electron microscope (FESEM) and thermal mechanical analyzer (TMA). Results indicate that the structural phase transition of the Yb_2?xLa_xW₃O₁₂ changes from orthorhombic to monoclinic with increasing substituted content of lanthanum. The pure phases can form in the composition range of 0 ≤ x < 0.5 with orthorhombic structure and 1.5 < x ≤ 2 with monoclinic one. High lanthanum content leads to a low hygroscopicity of Yb_2?xLa_xW₃O₁₂. Negative thermal coefficients of the Yb_2?xLa_xW₃O₁₂ (0 ≤ x ≤ 2) also vary from ?7.78 × 10^?6 K^?1 to 2.06 × 10^?6 K^?1 with increasing substituted content of lanthanum.     

Mass spectrometric study of the laser-evaporated Fe–Zr–O system up to 3300 K

Material systems such as U–Zr–O, Fe–Zr–O, and Zr–O have been recognized as fundamental for the analysis of in-vessel nuclear fuel debris behavior during a severe meltdown accident. In the present work, the evaporation behavior of ZrO₂ and Zr–Fe–O systems are investigated using heating with laser pulses of millisecond duration and time-of-flight mass spectrometry. The relative partial pressures of main species of vapor over ZrO₂ and ZrO₂–FeO systems were measured at temperatures above 2750 K. The temperature dependence of O/Zr atomic ratio in vapor over zirconia was analyzed: it turned out that evaporation occurs in a noncongruent mode at temperatures above 3000 K. Evaporation of the Zr–Fe–O system was greatly affected by the fast evaporation of FeO, implying that the atomic Zr/Fe ratio, less than 0.1 below 3000 K, significantly increased with temperature. Moreover, the ratios of main vapor components were defined only by the surface temperature, independent of the zirconia sample origin.