Correlation between acidic properties of nickel sulfate supported on TiO2-ZrO2 and catalytic activity for ethylene dimerization

A series of catalysts, NiSO₄/TiO₂-ZrO₂, for ethylene dimerization was prepared by the impregnation method using an aqueous solution of nickel sulfate. For NiSO₄/TiO₂ -ZrO₂ sample, no diffraction line of nickel sulfate was observed up to 30 wt%, indicating good dispersion of nickel sulfate on the surface of TiO₂-ZrO₂. The addition of nickel sulfate to TiO₂-ZrO₂ shifted the phase transition of TiZrO₄ from amorphous to orthorhombic to a higher temperature because of the interaction between nickel sulfate and TiO₂-ZrO₂. The number of acid sites of NiSO₄/TiO₂-ZrO₂ increased in proportion to the nickel sulfate content up to 20 wt% of NiSO₄. Nickel sulfate supported on TiO₂-ZrO₂ was found to be very active even at room temperature, giving a maximum in both activity and acidity when the catalyst containing 20% NiSO₄ was calcined and evacuated at 500°C The asymmetric stretching frequency of the S=O bonds for NiSO₄/TiO₂-ZrO₂ samples was related to the acidic properties and catalytic activity. That is, the higher the frequency, the higher both the number of acid sites and the catalytic activity for ethylene dimerization.     

Volatilization of fluorine in a CaO–SiO2–CaF2-based system with the substitution of Na2O with K2O

Cuspidine-based systems are used to control the crystallization in mold fluxes, which is enabled by CaF₂ additions. However, excess CaF₂ increases the corrosion of casting machines. Therefore, Na₂O and K₂O are added to the mold flux system to ensure an optimized crystallization and lubrication ability of the flux with the CaF₂ content. This study investigated the effect of substituting Na₂O with K₂O on the volatilization of fluorine in a CaO–SiO₂–CaF₂-based slag system at high temperatures. The substitution of Na₂O with K₂O was performed at 5 mol% intervals. The volatilization was observed by thermogravimetric analysis under several isothermal conditions. The mass loss was measured at a heating rate of 5, 10, and 20 K/min. As the temperature increased, the volatilization of the mixed samples increased. The activation energy was calculated using the Flynn–Wall–Ozawa and Kissinger–Akahira–Sunose methods. A kinetic analysis of the volatilization of fluorine was conducted using the calculated parameters and several known kinetic models. Consequently, the volatilization of the Na-rich sample was controlled by chemical reactions and that of the K-rich sample was identified to be controlled by a phase-boundary-controlled reaction. These results suggest that the addition of mixed alkali oxide promote the volatilization during the early stages of the reaction. From the post-experimental composition analyses, the remaining Na and K in the samples suggested a different mechanism for the Na and K volatilization. The volatilization of Na increased with time, whereas K volatilized easily during the beginning of the reaction.     

Bismuth sulfide and its carbon nanocomposite for rechargeable lithium-ion batteries

Bi₂S₃ and Bi₂S₃/C nanocomposites prepared by high-energy mechanical milling were evaluated as electrode materials in lithium secondary batteries. For a Bi₂S₃/C nanocomposite, Bi₂S₃ nanocrystallites were well distributed in an amorphous carbon matrix. The reaction mechanism of the Bi₂S₃/C electrode was also examined during the first cycle. The Bi₂S₃/C nanocomposite anode showed superior electrochemical performance (ca. 500 mAh g⁻¹ and 85% of the capacity retention over 100 cycles).     

Radiation-induced synthesis of solid alkaline exchange membranes with quaternized 1,4-diazabicyclo[2,2,2] octane pendant groups for fuel cell application

In this study, anion exchange membranes having various quaternary ammonium groups were prepared by using a radiation-induced graft polymerization method and followed by subsequent treatment of films with amines. FT-IR and SEM-EDX techniques were employed to monitor the reaction progress. The cross-sectional distribution of the anionic exchange functional groups through the membranes has also been investigated using SEM-EDX technique. The results reveal that the anion exchange groups were found to be evenly distributed throughout the membranes. It was also observed that the physico-chemical properties of the anion exchange membranes such as water uptake, ionic conductivity, thermal stability, chemical stability, mechanical properties, and dimensional stability are largely influenced by the chemical structure of the quaternary ammonium moiety which is attached to the graft chains. Among the prepared anion exchange membranes, the membrane having mono-quaternized 1,4-diazabicyclo[2,2,2]octane moiety was found to have both enhanced chemical and dimensional stabilities, while the others having quaternized trimethylamine or bis-quaternized 1,4-diazabicyclo[2,2,2]octane have the decreased dimensional and chemical stabilities.     

Improved reutilization of industrial crude lysine to 1,5-diaminopentane by enzymatic decarboxylation using various detergents and organic solvents

World-wide production of l-lysine has rapidly increased in recent years. In the industrial scale production, it is cost effective to minimize waste as many waste materials are generated during downstream processing. Therefore, the conversion of crude lysine to a more valuable product reduces waste emission. In this study, 1,5-diaminopentane (DAP, trivial name: cadaverine) was produced by l-lysine decarboxylation using Hafnia alvei. The conditions of enzymatic reaction were determined. In particular, the addition of specific detergent (Brij 56) was significantly affected in the bioconversion system. Addition of hydrophobic organic solvent improved the mixing of the reactants. Finally, an industrial crude form of lysine served as a substrate. The DAP conversion by analytical, feed and industrial crude l-lysine was 93.9%, 90.3%, and 63.8%, respectively.     

Analysis and estimation of yield strength of API X80 linepipe steel pipe by low-cycle fatigue tests

In the present study, spiral piping was conducted on API X80 linepipe steel, and the outer and inner wall pipe yield strengths were measured. A low-cycle fatigue test was conducted on a leveled X80 steel sheet to simulate piping and flattening processes, and the strain hardening and Bauschinger effects, induced from different strain histories, were evaluated and combined using Swift??s equation and the Bauschinger stress parameter, respectively. By analyzing the stress-strain curves obtained from the low-cycle fatigue test, the yield strengths of the outer and inner walls were estimated to be 592 MPa and 492 MPa, respectively, which are lower by 20?C80 MPa than that of the actual pipe used. Possible reasons for measured and estimated yield strength differences could be the simulation determining procedure of the pre-strain and Bauschinger stress parameters, preposition of same strain hardening behavior depending on strain history, and pre-strain differences depending on thickness location in the steel sheet during piping.     

Interdiffusion Between Zr Diffusion Barrier and U-Mo Alloy

U-Mo alloys are being developed as low-enrichment uranium fuels under the Reduced Enrichment for Research and Test Reactor (RERTR) program. Significant reactions have been observed between U-Mo fuels and Al or Al alloy matrix. Refractory metal Zr has been proposed as barrier material to reduce the interactions. In order to investigate the compatibility and barrier effects between U-Mo alloy and Zr, solid-to-solid U-10wt.%Mo versus Zr diffusion couples were assembled and annealed at 600, 700, 800, 900, and 1000?°C for various times. The microstructures and concentration profiles due to interdiffusion and reactions were examined via scanning electron microscopy and electron probe microanalysis, respectively. Intermetallic phase Mo₂Zr was found at the interface, and its population increased when annealing temperature decreased. Diffusion paths were also plotted on the U-Mo-Zr ternary phase diagrams with good consistency. The growth rate of interdiffusion zone between U-10wt.%Mo and Zr was also calculated under the assumption of parabolic diffusion and was determined to be about 10³ times lower than the growth rate of diffusional interaction layer found in diffusion couples U-10wt.%Mo versus Al or Al-Si alloy. Other desirable physical properties of Zr as barrier material, such as neutron adsorption rate, melting point, and thermal conductivity, are presented as supplementary information to demonstrate the great potential of Zr as the diffusion barrier for U-Mo fuel systems in RERTR.     

Isothermal oxidation of physical vapor deposited partially stabilized zirconia thermal barrier coatings

Thermal barrier coatings (TBCs), consisting of physical vapor deposited (PVD) partially stabilized zirconia (PSZ, 8 wt.%Y₂O₃) and a diffusion aluminide bond coat, were characterized as a function of time after oxidative isothermal heat treatment at 1373 K in air. The experimental characterizations was conducted by X-ray diffraction analysis and scanning electron microscopy (SEM) with energy-dispersive spectroscopy. During cooling to room temperature, spallation of the PSZ ceramic coatings occurred after 200 and 350 h of isothermal heat treatment. This failure was always sudden and violent, with the TBC popping from the substrate. The monoclinic phase of zirconia was first observed on the bottom surface of the PVD PSZ after 200 h of isothermal heat treatment. The failure of TBCs occurred either in the bond coat oxidation products of αAl₂O₃ and rutile TiO₂ or at the interface between the oxidation products and the diffusion aluminide bond coat or the PSZ coating.     

Aerodynamic performance optimization for the rotor design of a hovering agricultural unmanned helicopter

The importance of using Agriculture unmanned helicopters (AUHs), especially for spraying pesticides and fertilizers on any terrain type to ensure crop yields, has been recently acknowledged. Apart from flying these helicopters at a super-low altitude and low speed, using an efficient and optimum rotor blade ensures a uniform and deep penetration of pesticide and fertilizers over a specified area. Accordingly, this work attempts to optimize the rotor blade of an AUH by using coupling statistics and several numerical techniques, including design of experiments, response surface method, and computational fluid dynamics. The experiments are designed using the central composite design method and by selecting the geometric variables that affect the aerodynamic performance of the rotor blade, including the root chord, tip chord, and angle of attack. The angle at the root and tip is optimized in order for the resulting twist to produce a uniform blade loading, achieve maximum lift, and minimize the required hover power. The required aerodynamic forces and limited availability of engine power are identified as constraints. The blade is optimized only when the helicopter is hovering at a persistent rotational speed, and the hover efficiency of the rotor blade with an optimal twist distribution is significantly higher than the baseline.