Thermal and photon effects on the reaction of H2 and O2 to water over Ag–Pd/TiO2

The reaction of H₂ and O₂ to water are studied over a Ag–Pd/TiO₂ anatase catalyst, under dark and photo-irradiation conditions in the gas and liquid phases. The catalyst consisted of metal particles of mean size of ca.1 nm dispersed over 10–15 nm TiO₂ particles. Kinetic parameters including order of reaction (n), rate constant (k), and activation energy (E_a), were evaluated. E_a for the thermal reaction was found to be 49-47 kJ mol^?1. The oxidation reaction rate constant was found to be ca. 3 times higher in the presence of photons when compared to dark reaction at room temperature. The overall quantum yield of the reaction in the slurry phase was found to be 0.09. Considering the number of metal particles on TiO₂, the photon yield per metal particle was found to be 0.16. A possible explanation of the changes in kinetics with respect to experimental conditions is given.     

Effects on the crystallite growth behavior of LaPO4 nanopowders and its mechanical properties

The effects of pH of the reaction solution and the concentration of phosphoric acid on the crystal growth behavior of LaPO₄ crystallites were investigated and the mechanical properties of rare-earth phosphates were compared. As a result, the concentration of phosphoric acid of 10% was beneficial to the crystal growth of LaPO₄ nanocrystalline. When the pH value of the reaction solution was 2, the size of LaPO₄ crystallites increased gradually with the increasing reaction temperature, and the smallest crystallite size of 43.27 nm was obtained after heat-treatment at 1000 °C. Simultaneously, the activation energy for crystal growth of LaPO₄ nanocrystalline was relatively lower (26.82 kJ mol⁻¹). With the decreasing radii of rare-earth ions, the hardness, Young's modulus and fracture toughness of the bulk rare-earth phosphates exhibited a reduced tendency, resulted from the increase of porosity under the same preparation process.     

Rapid synthesis of garnet-type Li7La3Zr2O12 solid electrolyte with superior electrochemical performance

Li₇La₃Zr₂O₁₂-based garnet-type solid electrolytes are promising candidates for use in all-solid-state lithium batteries (ASSLBs). However, their potential in large-scale commercial applications is largely hindered by the time/energy-consuming and lithium-wasting synthetic method which typically needs a long-duration high temperature solid state reaction process. Herein we invent a fast preparation route that involves a short-period thermal reaction (1100 °C for 10 min) in laboratory muffle furnaces following by conventional hot pressing technique to get almost fully dense (Al, Ga, Ta, Nb)-doped garnet-type electrolytes with high phase purity (>99.9 %). The large and compact grains, low porosity and high phase purities of garnet ceramic electrolytes synthesized in this study ensure superior electrochemical performance. Particularly, Ga-doped cubic Li₇La₃Zr₂O₁₂ shows extremely low E_a values (0.17?0.18 eV) and record-high lithium ionic conductivities (>2 × 10^?3 S cm^-1 at 25 °C).     

Synthesis and characterization of hydrogenated novel AlCrFeMnNiW high entropy alloy

A novel high entropy alloy (HEA) i.e. AlCrFeMnNiW is synthesized via high-energy planetary ball milling with an average crystallite size of 10.37 nm. The morphology study of hydrogenated and dehydrogenated HEA is carried out through Scanning Electron Microscope (SEM). The HEA is charged with hydrogen using inhouse Sievert's Apparatus which results to be maximum hydrogen storage capacity of 0.615 wt% at atmospheric pressure and temperature. The dehydrogenation of the sample is performed through thermogravimetry (TG) at different scanning rate. The crystalline structure (i.e. lattice parameters) and chemical composition of HEA is studied using X-Ray Diffraction (XRD) and Energy Dispersive X-Ray analysis (EDX) respectively. The unit cell volume of as-prepared alloy is estimated as 0.03131 nm³ whereas the average crystallite size as 10.37 nm. It is observed that the unit cell volume is increased by 0.67% and crystallite size decreased by 10.8% upon hydrogenation whereas it is then decreased by 0.2% and increased by 6.7% respectively upon dehydrogenation. Activation energy during hydrogen desorption is found to be −8.161 kJ/mol. The enthalpy and entropy of the mixing are estimated to be −2.645 kJ/mol and 1.793 R J/mol K.     

Hydrogen storage property of as-milled La7RE3Mg80Ni10 (RE = Sm,Ce) alloys

Element replacement and mechanical milling are considered as the most effective ways to improve Mg-based alloys in their hydrogen storage performance. The as-milled La₇RE₃Mg₈₀Ni₁₀ (RE = Sm, Ce) alloys were prepared in this experiment by introducing both element replacement (replacing La by Ce or Sm partially) and mechanical milling technologies. The influence made by different replacing elements on the structure and hydrogen storage property of La₇RE₃Mg₈₀Ni₁₀ (RE = Sm, Ce) alloys was investigated in detail. X-ray diffraction, transmission electron microscope, automatic Sievert apparatus, thermogravimetry and differential scanning calorimetry were used to investigate the experimental alloys. The experiment reveals that a nanocrystalline and amorphous structure appears after mechanical milling. Moreover, comparing with the RE = Sm alloy, the RE = Ce alloy has a superior hydrogen desorption property, including larger hydrogen absorption capacity, faster hydriding/dehydriding rate, lower onset hydrogen desorption temperature, and lower dehydrogenation activation energy.     

Improved ball milling method for the synthesis of nanocrystalline TiFe compound ready to absorb hydrogen

In this study, we propose a method to produce nanocrystalline TiFe powder by high-energy ball milling, in order to avoid the common sticking problem of the material to the milling tools, assuring a material prompt to absorb hydrogen as well. The method consists of making a preliminary milling operation with the elemental powders (50:50 stoichiometric ratio) to form a strong adhered layer of the milled material on the surfaces of the vial and balls. The main milling operation is then performed with a new powder charge (same composition as before), but now adding a process control agent (stearic acid). Various processing times - 2, 6, 10 and 20 h - were used in the milling experiments. Nanocrystalline TiFe was synthesized in this way with low oxygen contamination, full yields for milling times of 6 h or over, requiring no heat treatments for the first hydrogen absorption. Hydrogen storage capacity of 1.0 wt% at room temperature under 20 bar was attained by the sample milled for 6 h. Kinetic data from samples milled for 2 h and 6 h agreed with Jander model for the rate limiting step of the hydriding reaction, which is based on diffusion with constant interface area.     

Kinetic analysis of magnesium aluminate spinel formation: Effect of MgO:Al2O3 ratio and titania dopant

The mechanistic pathway of MgO-Al₂O₃ reaction in solid state to form MgAl₂O₄ spinel was investigated to correlate the kinetic parameters with ratio of reactants (MgO:Al₂O₃) and with the presence of a doping agent, TiO₂. The time-temperature-expansion data of oxide compacts was analyzed using several model free analyses and model based (linear and non-linear) kinetic algorithms. These indicated that spinel formation process can be best described by single step with n-dimensional Avrami equation for every MgO:Al₂O₃ ratio, irrespective of titania dopant. The activation energy (E_a) of the process was proportional to % spinel formed in each system and validated with quantitative XRD analysis. The higher value of Avrami coefficient (n) in 90 wt% Al₂O₃ compositions has been explained with geometric considerations of powder packing. Incorporations of 1% TiO₂ in the MgO: Al₂O₃ oxide compact did not markedly affect the reaction model, frequency factor and Activation energy.     

Influence of processing conditions on the ionic conductivity of holmium zirconate (Ho2Zr2O7)

Nanopowders of holmium zirconate (Ho₂Zr₂O₇) synthesised through carbon neutral sol-gel method were pressed into pellets and individually sintered for 2 h in a single step sintering (SSS) process from 1100 °C to 1500 °C at 100 °C interval and in a two step sintering (TSS) process at (I) −1500 °C for 5 min followed by (II) - 1300 °C for 96 h. Relative density of each of the sintered pellet was determined using the Archimedes’ technique and the theoretical density was calculated from crystal structure data. Grain size was obtained from SEM micrographs using ImageJ. Pellets processed by TSS have been found to be denser (98 %) with less grain growth (1.29 μm) as compared to the pellets processed using SSS process. Ionic conductivity of Ho₂Zr₂O₇ pellets sintered by two different processes was measured using ac impedance spectroscopy technique over the temperature range of 350 °C–750 °C in the frequency range of 100 mHz–100 MHz for both heating and cooling cycles. The temperature dependence of bulk (2.67⨯10⁻³ Scm⁻¹) and grain boundary (2.50⨯10⁻³ Scm⁻¹) conductivities of Ho₂Zr₂O₇ prepared by TSS process are greater than those processed by SSS process suggesting the strong influence of processing conditions and grain size. Results of this study, indicates that the TSS is the preferable route for processing the holmium zirconate as it can be sintered to exceptionally high densities at lower temperature, exhibits less grain growth and enhanced ionic conductivity compared with the samples processed by SSS process. Hence, holmium zirconate can be considered as a promising new oxide ion conducting solid electrolyte for intermediate temperature SOFC applications between 350 °C and 750 °C temperature range.     

压水堆核电厂一回路首次钝化工艺研究

压水堆核电厂热态功能试验中的一回路首次钝化对核电厂一回路材料腐蚀控制和减少腐蚀产物等方面具有重要作用。本文结合理论研究与工程实际情况，提出了在热态功能试验过程中钝化膜的生成包含电化学反应和化学反应的观点，阐述了双层膜的生长机理，解释了用电化学测试方法分析钝化工艺过程的合理性，推导出钝化温度与钝化膜反应速率的函数关系式，钝化温度升高，反应速率升高，钝化时间缩短；明确了钝化工艺温度的理论限值应不低于260℃。      

Exactly satisfying initial conditions neural network models for numerical treatment of first Painlevé equation

In this paper, novel computing approach using three different models of feed-forward artificial neural networks (ANNs) are presented for the solution of initial value problem (IVP) based on first Painlevé equation. These mathematical models of ANNs are developed in an unsupervised manner with capability to satisfy the initial conditions exactly using log-sigmoid, radial basis and tan-sigmoid transfer functions in hidden layers to approximate the solution of the problem. The training of design parameters in each model is performed with sequential quadratic programming technique. The accuracy, convergence and effectiveness of the proposed schemes are evaluated on the basis of the results of statistical analyses through sufficient large number of independent runs with different number of neurons in each model as well. The comparisons of these results of proposed schemes with standard numerical and analytical solutions validate the correctness of the design models.