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.     

Synergistic effect of co-alloying elements on site preferences and elastic properties of Ni3Al: A first-principles study

The site preferences of co-alloying elements (Mo–Ta, Mo–Re, Mo–Cr) in Ni₃Al are studied using first-principles calculations, and the effects of these alloying elements on the elastic properties of Ni₃Al are evaluated by elastic property calculations. The results show that the Mo–Ta, Mo–Re and Mo–Cr atom pairs all prefer Al–Al sites and the spatial neighbor relation of substitution sites almost has no influence on the site preference results. Furthermore, the Young's modulus of Ni₃Al increases much higher by substituting Al–Al sites with co-alloying atoms, among which Mo–Re has the best strengthening effect. The enhanced chemical bondings between alloying atoms and their neighbor host atoms are considered to be the main strengthening mechanism of the alloying elements in Ni₃Al.     

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.     

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.     

Material design and development: From classical thermodynamics to CALPHAD and ICME approaches

This paper presents an overview and examples of material design and development using (1) classical thermodynamics; (2) CALPHAD (calculation of phase diagrams) modeling; and (3) Integrated Computational Materials Engineering (ICME) approaches. Although the examples are given in lightweight aluminum and magnesium alloys for structural applications, the fundamental methodology and modeling principles are applicable to all materials and engineering applications. The examples in this paper have demonstrated the effectiveness and limitations of classical thermodynamics in solving specific problems (such as nucleation during solidification and solid-state precipitation in aluminum alloys). Computational thermodynamics and CALPHAD modeling, when combined with critical experimental validation, have been used to guide the selection and design of new magnesium alloys for elevated-temperature applications. The future of material design and development will be based on a holistic ICME approach. However, key challenges exist in many aspects of ICME framework, such as the lack of diffusion/mobility databases for many materials systems, limitation of current microstructural modeling capability and integration tools for simulation codes of different length scales.     

Alloy optimisation of bainitic steel for large plastic mould

Based on the phase transformation theories, especially the T₀ concept of bainite transformation, alloy optimisation of bainitic steel with carbides has been carried out aiming at the produce of plastic mould with large cross-section. The effect of manganese and silicon on proeutectoid ferrite and bainite transformation is explored by dilatometric analysis, XRD and different microscopy techniques. The results show that after the alloy optimisation, the transformation of proeutectoid ferrite is suppressed and when the cooling rate is lower than 0·1°C?s^??1, the new lower bainite transformation appears by decreasing carbon capacity of austenite and promoting carbide precipitation. Industrial production proves that the optimised alloy SDP1 can meet the demand for the plastic mould with the thickness of 1050?mm.     

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.     

Effects of Rare Earths on Toughness of 31Mn2SiRE Wear-Resistance Cast Steel

The toughness of 31Mn2SiRE wear-resistance cast steel were increased by means of RE compound modification and high temperature austenitizing. The results show that the microstructures can be refined, needle and network ferrite are eliminated, the dislocation density and the quantity of dislocated martensite are increased remarkably, and the shape and distribution of inclusions are improved by the addition of RE. Therefore, the mechanical properties of the modified steel can be greatly increased, especially the toughness (αK) by 44%, yield strength (σs) by 10%, and elongation (δ5) by 42%.