Size-controlled synthesis of Mo powders via hydrogen reduction of MoO2 powders with the assistance of Mo nuclei

The size-controlled preparation of Mo powders is always a challenge and important task in the molybdenum metallurgy. In the current study, Mo powders with controllable sizes are synthesized by hydrogen reduction of MoO₂ powders with the assistance of Mo nuclei in the range of 900–1100 °C. The influences of the particle sizes of Mo nuclei, the additive amount as well as reaction temperature on the morphology and particle sizes of the final products are studied. For the hydrogen reduction of MoO₂ without any additive, the obtained Mo powders always have large particle sizes. However, the addition of small amounts of nuclei in MoO₂ can help Mo nucleate dispersedly, and the growth of Mo could be also controlled by adjusting the sizes of added nuclei, amount of addition and the reaction temperature. With the addition of Mo nuclei, the different sizes of Mo powders with the good dispersity can be prepared. As adding commercial Mo powders with the particle size of about 2.03 μm, the micron-sized Mo powders ranged from 2.11 μm to 3.25 μm could be prepared. While for the case of adding ultrafine Mo nuclei of about 170 nm, Mo powders from 0.28 μm to 0.88 μm can be obtained. Moreover, the more the amounts of nuclei added and the lower the reaction temperature (in the range of 900–1100 °C) is, the smaller the particle size of the prepared Mo powder will be. The current method is a facile and feasible method, and is potential to be used for industrial production of Mo powder with controllable particle sizes.     

Synthesis of NaYF4:20% Yb3+,2% Er3+,2% Ce3+@NaYF4 nanorods and their size dependent uptake efficiency under flow condition

Lanthanide doped fluorescent nanoparticles have gained considerable attention in biomedical applications. However, the low uptake efficiency of nanoparticles by cells has limited their applications. In this work, we demonstrate how the uptake efficiency is affected by the size of nanoparticles under flow conditions. Using the same size NaYF₄:20% Yb³⁺,2% Er³⁺,2% Ce³⁺ (the contents of rare earths elements are in molar fraction) nanoparticles as core, NaYF₄:20% Yb³⁺,2% Er³⁺,2% Ce³⁺@NaYF₄ core–shell structured nanorods (NRs) with different sizes of 60–224 nm were synthesized by thermal decomposition and hot injection method. Under excitation at 980 nm, a strong upconversion green emission (541 nm, ²H_11/2 → ⁴I_15/2 of Er³⁺) is observed for all samples. The emission intensity for each size nanorod was calibrated and is found to depend on the width of NRs. Under flow conditions, the nanorods with 96 nm show a maximum uptake efficiency by endothelial cells. This work demonstrates the importance of optimizing the size for improving the uptake efficiency of lanthanide-doped nanoparticles.     

Controlled chemical modification of the internal surface of photonic crystal fibers for application as biosensitive elements

Photonic crystal fibers (PCF) are one of the most promising materials for creation of constructive elements for bio-, drug and contaminant sensing based on unique optical properties of the PCF as effective nanosized optical signal collectors. In order to provide efficient and controllable binding of biomolecules, the internal surface of glass hollow core photonic crystal fibers (HC-PCF) has been chemically modified with silanol groups and functionalized with (3-aminopropyl) triethoxysilane (APTES). The shift of local maxima in the HC-PCF transmission spectrum has been selected as a signal for estimating the amount of silanol groups on the HC-PCF inner surface. The relationship between amount of silanol groups on the HC-PCF inner surface and efficiency of following APTES functionalization has been evaluated. Covalent binding of horseradish peroxidase (chosen as a model protein) on functionalized PCF inner surface has been performed successively, thus verifying the possibility of creating a biosensitive element.     

Nanostructured hydrogen storage materials prepared by high-energy reactive ball milling of magnesium and ferrovanadium

Hydrogen storage nanocomposites prepared by high energy reactive ball milling of magnesium and vanadium alloys in hydrogen (HRBM) are characterised by exceptionally fast hydrogenation rates and a significantly decreased hydride decomposition temperature. Replacement of vanadium in these materials with vanadium-rich Ferrovanadium (FeV, V80Fe20) is very cost efficient and is suggested as a durable way towards large scale applications of Mg-based hydrogen storage materials. The current work presents the results of the experimental study of Mg–(FeV) hydrogen storage nanocomposites prepared by HRBM of Mg powder and FeV (0–50 mol.%). The additives of FeV were shown to improve hydrogen sorption performance of Mg including facilitation of the hydrogenation during the HRBM and improvements of the dehydrogenation/re-hydrogenation kinetics. The improvements resemble the behaviour of pure vanadium metal, and the Mg–(FeV) nanocomposites exhibited a good stability of the hydrogen sorption performance during hydrogen absorption – desorption cycling at T = 350 °C caused by a stability of the cycling performance of the nanostructured FeV acting as a catalyst. Further improvement of the cycle stability including the increase of the reversible hydrogen storage capacity and acceleration of H₂ absorption kinetics during the cycling was observed for the composites containing carbon additives (activated carbon, graphite or multi-walled carbon nanotubes; 5 wt%), with the best performance achieved for activated carbon.     

Reacting flow coupling with thermal impacts in a single solid oxide fuel cell

Thermal impacts are the major concern for the designs of electrolyte of Solid Oxide fuel cells (SOFCs) due to the high temperature operating conditions. In this study, the coupling dynamics of electrochemical reacting flows with heat transfer and generations of thermal strains and stresses (thermal impact) of solid electrolyte and porous electrodes are investigated in a single SOFC by numerical simulations. Modeling results from a test case show that the coupling is necessary as the electrochemical and thermal properties of the cell strongly depends on temperature, meanwhile, the thermal strains and stresses on temperature gradients. The differences in current density and thermal strain gradients predicted by coupling and decoupling simulations are as larger as 20% because of the strong dependents of ionic conductivity of the electrolyte material on temperature, the maximum thermal strain, thermal stresses, and temperature are all about 5%. It is identified that the high operation voltage benefits to the thermal strain, which decreases 20% when the cell operating from 0.5 V–0.7 V.     

TiO2 nanoparticles with superior hydrogen evolution and pollutant degradation performance

The human life faces serious energy shortage and environmental pollution problems, therefore developing a facile and environmental friendly strategy for synthesizing nanoparticles (NPs) with improved photocatalytic activity could pave the way for different applications. In the present study, one-pot/in-situ fluorine-free synthesis process has been examined toward the solvothermal production of anatase TiO₂ nanoparticles with exposed facet orientation. This is an aim to achieve the excellent photocatalytic/photoelectrocatalytic performance. Most importantly addressing the global energy shortage, the synthesized TiO₂ NPs represent superior performance in photoelectrocatalytic water splitting toward hydrogen production. The overpotential required to drive the hydrogen evolution reaction was −391, −346 and −283 mV vs. Ag/AgCl for P25, cubic and truncated octahedral NPs, respectively. Additionally, TiO₂ NPs with exposed facets represent excellent photocatalytic performance toward environmental purification. As synthesized nanoparticles was examined via photocatalytic degradation of Acid Blue 5 and photocatalytic removal of NO gas. The enhanced photocatalytic and photoelectrocatalytic performance are associated to the effect of exposed facet orientation of final nanoparticles.     

High temperature X-ray diffraction study of the kinetics of phase separation in hypostoichiometric uranium–plutonium mixed oxides

Uranium–plutonium mixed oxides incorporating high amounts of plutonium are considered for future nuclear reactors. For plutonium content above 20%, a phase separation occurs, depending on the temperature and on the oxygen stoichiometry. Here, using an in situ fast X-ray diffraction device dedicated to radioactive materials, we evidenced a phase separation occurring during rapid cooling from 1773 K to room temperature at the rates of 0.05 and 2 K s⁻¹ for two (U_1−yPu_y)O_2−x compounds, with y = 0.28 and 0.45, under a reducing atmosphere. Optical microscopy reveals that the cooling rate impacts the microstructure of the fuel pellet by inducing severe macroscopic cracks. These results are important for using uranium–plutonium mixed oxides with high plutonium content as nuclear fuels. Considering the associated issues, they dictate a cautious attitude when defining their conditions of fabrication.     

Thermal,mechanical and electrical properties of hard B4C,BCN, ZrBC and ZrBCN ceramics

We study the thermal, mechanical and electrical properties of B₄C, BCN, ZrBC and ZrBCN ceramics prepared in the form of thin films by magnetron sputtering. We focus on the effect of Zr_x(B₄C)_1−x sputter target composition, the N₂+Ar discharge gas mixture composition, the deposition temperature and the annealing temperature after the deposition. The thermal properties of interest include thermal conductivity (observed in the range 1.3–7.3 W m⁻¹ K⁻¹), heat capacity (0.37–1.6×10³ J kg⁻¹ K⁻¹ or 1.9–4.1×10⁶ Jm⁻³ K⁻¹), thermal effusivity (1.6–4.5×10³ J m⁻² s^−1/2 K⁻¹) and thermal diffusivity (0.38–2.6×10⁻⁶ m² s⁻¹). We discuss the relationships between materials composition, preparation conditions, structure, thermal properties, temperature dependence of the thermal properties and other (mechanical and electrical) properties. We find that the materials structure (amorphous×crystalline hexagonal ZrB₂-like×nanocrystalline cubic ZrN-like), more than the composition, is the crucial factor determining the thermal conductivity and other properties. The results are particularly important for the design of future ceramic materials combining tailored thermal properties, mechanical properties, electrical conductivity and oxidation resistance.     

Studies on rheological properties of methyltriethoxysilane (MTES) based flexible superhydrophobic silica aerogels

The flexible and superhydrophobic properties of silica aerogels are extremely important requirements for their long-term applications. Therefore, the present paper deals with the synthesis and characterization of flexible and superhydrophobic silica aerogels utilizing a two-step acid–base catalyzed sol–gel process with a novel precursor, methyltriethoxysilane (MTES), followed by supercritical drying. Solvent and catalysts used for the synthesis were methanol (MeOH), oxalic acid (C₂H₂O₄) and ammonium hydroxide (NH₄OH), respectively. Silica alcosol was prepared by varying the MeOH/MTES molar ratio (S) from 6.45 to 19.35 by keeping the each of oxalic acid (0.001 M)/MTES and maintaining a constant ammonium hydroxide (10 M)/MTES molar ratio at 4. It was observed that the Young’s modulus (Y) decreased from 15.03 × 10⁴ to 3.95 × 10⁴ N/m² with an increase in S value from 6.45 to 19.35. Utilizing constant molar ratio of MeOH/MTES at 19.35, experiments produced monolithic, less shrinkage and flexible aerogels. The effect of various sol–gel parameters such as acid and base catalysts concentration and gel-aging on the flexibility and hydrophobicity of the aerogels were investigated. The aerogels have been characterized by bulk density, percentage of volume shrinkage, Young’s modulus, elastic limit measurements, strain energy, Poisson’s ratio and contact angle measurements. The microstructural studies were carried out using Transmission Electron Microscopy. The hydrophobicity was confirmed by Fourier Transform Infrared (FTIR) spectroscopy.     

Magnetic properties of polyaniline doped with FeCl3

Magnetic properties of polyaniline (PANI) doped with FeCl₃ were investigated as a function of temperature and magnetic field. The temperature dependence of the magnetic susceptibility (χ) of PANI doped with FeCl₃ exhibits dominant paramagnetic component (well described by Curie–Weiss law with a negative Curie–Weiss temperature Θ) accompanied by a small temperature-independent paramagnetic contribution. Magnetization measured as the function of magnetic field shows smaller saturation effect than expected for non-interacting iron ions. These two observations suggest weak antiferromagnetic (AF) interactions between Fe ions.