New horizon in mechanochemistry—high-temperature,high-pressure mechanical synthesis in a planetary ball mill—with magnesium hydride synthesis as an example

A new route of materials synthesis, namely, high-temperature, high-pressure reactive planetary ball milling (HTPRM), is presented. HTPRM allows for the mechanosynthesis of materials at fully controlled temperatures of up to 450 °C and pressures of up to 100 bar of hydrogen. As an example of this application, a successful synthesis of magnesium hydride is presented. The synthesis was performed at controlled temperatures (room temperature (RT), 100, 150, 200, 250, 300, and 325 °C) while milling in a planetary ball mill under hydrogen pressure ($>$50 bar). Very mild milling conditions (250 rpm) were applied for a total milling time of 2 h, and a milling vial with a relatively small diameter (φ = 53 mm, V = ～0.06 dm³) was used. The effect of different temperatures on the synthesis kinetics and outcome were examined. The particle morphology, phase composition, reaction yield, and particle size were measured and analysed by scanning electron microscopy, X-ray diffraction, differential scanning calorimetry (DSC) techniques. The obtained results showed that increasing the temperature of the process significantly improved the reaction rate, which suggested the great potential of this technique for the mechanochemical synthesis of materials.     

The effect of Na addition on the first hydrogen absorption kinetics of cast hypoeutectic Mg–La alloys

With superior properties of Mg such as high hydrogen storage capacity (7.6 wt% H/MgH₂), low price, and low density, Mg has been widely studied as a promising candidate for solid-state hydrogen storage systems. However, a harsh activation procedure, slow hydrogenation/dehydrogenation process, and a high temperature for dehydrogenation prevent the use of Mg-based metal hydrides for practical applications. For these reasons, Mg-based alloys for hydrogen storage systems are generally alloyed with other elements to improve hydrogen sorption properties. In this article, we have added Na to cast Mg–La alloys and achieved a significant improvement in hydrogen absorption kinetics during the first activation cycle. The role of Na in Mg–La has been discussed based on the findings from microstructural observations, crystallography, and first principles calculations based on density functional theory. From our results in this study, we have found that the Na doped surface of Mg–La alloy systems have a lower adsorption energy for H₂ compared to Na-free surfaces which facilitates adsorption and dissociation of hydrogen molecules leading to improvement of absorption kinetic. The effect of Na on the microstructure of these alloys, such as eutectic refinement and a density of twins is not highly correlated with absorption kinetics.     

Polyetherimide-LaNi5 composite films for hydrogen storage applications

This study investigates the preparation of polyetherimide (PEI) – LaNi₅ composites films for hydrogen storage. Prior to the polymer addition, LaNi₅ was ball-milled at different conditions (250, 350, and 450 RPM) and annealed at 500 °C for 1 h under vacuum. The composites were produced with BM-LaNi₅-350 (PEI/LaNi₅-350) and annealed BM-LaNi₅-350 (PEI/LaNi₅-350-TT). Membranes were successfully produced through solvent casting assisted by an ultrasonic bath. The particles dispersion and the film morphology did not change after hydrogenation cycles. In the H₂ sorption experiments at 43 °C and 20 bar, the films stored H₂ without incubation time; both samples reached a capacity of ~0.6 wt%. The H₂ sorption kinetics of PEI/LaNi₅-350 was comparable to that of BM-LaNi₅-350, whereas PEI/LaNi₅-350-TT presented significantly slower kinetics. LaNi₅ oxidation was hindered by PEI, showing that it can be explored to improve metal hydrides air resistance. The results demonstrated that PEI films filled with LaNi₅ are promising materials for hydrogen storage.     

Effect of Ni/tubular g-C3N4 on hydrogen storage properties of MgH2

Additive doping is one of the effective methods to overcome the shortcomings of MgH₂ on the aspect of relatively high operating temperatures and slow desorption kinetics. In this paper, hollow g-C₃N₄ (TCN) tubes with a diameter of 2 μm are synthesized through the hydrothermal and high-temperature pyrolysis methods, and then nickel is chemically reduced onto TCN to form Ni/TCN composite at 278 K. Ni/TCN is then introduced into the MgH₂/Mg system by means of hydriding combustion and ball milling. The MgH₂–Ni/TCN composite starts to release hydrogen at 535 K, which is 116 K lower than the as-milled MgH₂ (651 K). The MgH₂–Ni/TCN composite absorbs 5.24 wt% H₂ within 3500 s at 423 K, and takes up 3.56 wt% H₂ within 3500 s, even at a temperature as low as 373 K. The apparent activation energy (E_a) of the MgH₂ decreases from 161.1 to 82.6 kJ/mol by the addition of Ni/TCN. Moreover, the MgH₂–Ni/TCN sample shows excellent cycle stability, with a dehydrogenation capacity retention rate of 98.0% after 10 cycles. The carbon material enhances sorption kinetics by dispersing and stabilizating MgH₂. Otherwise, the phase transformation between Mg₂NiH₄ and Mg₂NiH_0.3 accelerates the re/dehydrogenation reaction of the composite.     

The effect of synthesis conditions on the physicochemical properties of magnesium aluminate materials

Magnesium aluminate-based materials were prepared by applying different methods: (i) mechanochemical milling of the initial mixture of magnesium and aluminium nitrate powders (in appropriate stoichiometric amounts) followed by heat treatment at temperatures of 650 °C and 850 °C and (ii) melting of the mixture of nitrate precursors at 240 °C followed by thermal treatment at 650 °C, 750 °C and 850 °C. The effect of synthesis method on the structure and morphology of the obtained solids was studied by using various techniques such as: nitrogen adsorption-desorption isotherms, powder XRD, IR spectroscopy and SEM. It was shown that the mechanochemical milling performed before calcination procedure leads to obtaining of nanocrystalline magnesium aluminate spinel phase at lower temperature of 650 °C in comparison with the method using thermal treatment only (at 750 °C). The obtained nanomaterials exhibit mesoporous structure.     

Enhancement of thermal,mechanical, ignition and damping response of magnesium using nano-ceria particles

Magnesium (Mg)-based nanocomposites owing to their low density and biocompatibility are being targeted for transportation and biomedical sectors. In order to support a sustainable environment, the prime aim of this study was to develop non-toxic magnesium-based nanocomposites for a wide spectrum of applications. To support this objective, cerium oxide nanoparticles (0.5?vol%, 1?vol%, and 1.5?vol%) reinforced Mg composites are developed in this study using blend-press-sinter powder metallurgy technique. The microstructural studies exhibited limited amounts of porosity in Mg and Mg-CeO₂ samples (< 1%). Increasing presence of CeO₂ nanoparticles (up to 1.5?vol%) led to a progressive increase in microhardness, dimensional stability, damping capacity and ignition resistance of magnesium. The compressive strengths increased with the increasing addition of the nanoparticles with a significant enhancement in the fracture strain (up to ~48%). Superior energy absorption was observed for all the composite samples prior to compressive fracture. Further, enhancement in thermal, mechanical and damping characteristics of pure Mg is correlated with microstructural changes due to the presence of the CeO₂ nanoparticles.     

氢化物原子荧光光谱法测定酱油中微量铅的方法研究

建立了一种快速、高效的QuEChERS-高效液相色谱-质谱联用法（QuEChERS-HPLC-MS/MS）测定谷类杂粮制品中脱氧雪腐镰刀菌烯醇（DON）、3-乙酰脱氧雪腐镰刀菌烯醇（3-ADON）、15-乙酰脱氧雪腐镰刀菌烯醇（15-ADON）和玉米赤霉烯酮（ZON）共4种真菌毒素。样品前处理采用乙腈-水溶剂提取，经Florisil+C18+无水硫酸镁净化后检测。以0.10%甲酸-乙腈作为流动相，在质谱检测器的多反应监测模式下进行分析。结果表明，4种真菌毒素在各自的线性范围内线性关系良好，相关系数R2均大于0.999，回收率在85.1%～102.0%，相对标准偏差（RSD）为2.11%～6.22%。该方法具有前处理简单、净化效果好、灵敏度高和检测速度快的优点，适用于谷类杂粮制品中DON、3-ADON、15-ADON 和ZON的分析和定量检测。     

Verhalten von Magnesiumlegierungen für Anwendungen im Fahrzeugbau bei mechanisch‐elektrochemischer Komplexbeanspruchung: Einfluss passivierender Deckschichten und Mechanismen der lokalen Schädigung

Behavior of Magnesium‐Alloys for Automotive Applications under Mechanical and Environmental Loading: Influence of Passivating Films and Mechanisms of Local Breakdown To assure an efficient design of components under cyclic loading, all available data concerning fatigue have to be observed. Therefore the influences of manufacturing on the material condition, the mechanical loads and environmental effects have to be analysed. Magnesium‐alloys are of special interest for lightweight applications because of their excellent strength‐density ratio. The corrosion resistance of magnesium‐alloys depends on the same factors that are critical to other metals. The alloys have a good stability to atmospheric exposure and a good resistance to attack by alkali, chromic and hydrofluoric acids. However, because of the electrochemical activity of magnesium, the relative importance of some factors is greatly amplified. The nature and composition of passive films formed on magnesium‐alloys depend on the prevailing conditions, viz. alloy‐composition, passivation potential, pH, electrolyte composition and temperature. Passive films may be damaged by local breakdown. Because of this, magnesium‐alloys suffer a degradation of their properties when exposed to an aqueous environment. The main topic of the present investigations is the verification of mechanisms of the local breakdown of the protecting film. At least two mechanisms are possible for this localization: mechanical breakdown by slip steps and electrochemical breakdown (for e.g. by the effects of chloride ions). Corrosion and passivation of different high purity alloys have been studied in different solutions (neutral, alkaline with specific anions and cations) using electrochemical techniques. The diecasted alloys were tested as produced and machined. The results clarified that depending on alloy/material and surface condition/corrosion environment different mechanisms for electrochemical breakdown of the protecting films are possible. Hence fatigue life under environmental loading is influenced by surface and testing conditions.     

Effect of Stoichiometry on Properties of Rare-Earth-Based Hydrogen Storage Alloy for Nickel-Metal Hydride Secondary Battery

Effect of stoichiometry on microstructures, electrochemical properties and PCT characteristics of the alloys MI(Ni0.71Co0.15-Al0.06Mn0.08)x (MI=Lanthanum-rich Michmetal, x=4.6~5.2) have been investigated. The lattice constants a, c, and cellvolumes of non-stoichiometric alloys are bigger than those of the stoichiometric alloy. With the increasing stoichiometry x,the value of a decreases, and the value of c and cell volume increases except for those of the stoichiometric alloy; the plateaupressure of PCT curve, discharge capacity and cycling stability all increase. The alloy with x=5.2 shows the highest dischargecapacity and the best cycling stability among the studied alloys.     

Effect of Synergistic Anticorrosion Treatments on Cycling Stability of Mg-Based Hydrogen Storage Electrode

In this paper, any two of the three anticorrosion agents, that is emulsifier (OP-10), soluble glass (Na2O·nSiO2) and glycerin (C3H8O3), were treated simultaneously on the surface of amorphous (a-) MgNi+5% Ml2Mg17 (Ml denotes the lanthanum-rich mish metal) electrode and the electrolyte. Effect of the synergistic anticorrosion treatment on charging/discharging cycle stability of the electrode was investigated. Contrasted with single treatment method, the cycling stability of the electrodes was further improved. The desirable synergistic anticorrosion method was that the electrode was treated by the soluble glass, and that OP-10 was added into the electrolyte. The cyclic voltammogram (CV) results of the electrode show clearly that the anticorrosion agent can change the electrochemical activity and mechanism of the electrode. The concentration of the anticorrosion agent in the electrolyte treated by the synergistic anticorrosion method was also investigated. The appropriate concentration of the anticorrosion agents in the electrolyte is 0.143%.