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.     

Identification and U-control of a state-space system with time-delay

This article presents a state-space model with time-delay to map the relationship between known input-output data for discrete systems. For the given input-output data, a model identification algorithm combining parameter estimation and state estimation is proposed in line with the causality constraints. Consequently, this article proposes a least squares parameter estimation algorithm, and analyzes its convergence for the studied systems to prove that the parameter estimation errors converge to zero under the persistent excitation conditions. In control system design, the U-model based control is introduced to provide a unilateral platform to improve the design efficiency and generality. A simulation portfolio from modeling to control is provided with computational experiments to validate the derived results.     

Achieving superior hydrogen storage properties via in-situ formed nanostructures: A high-capacity Mg–Ni alloy with La microalloying

Mg-based hydride is a promising hydrogen storage material, but its capacity is hindered by the kinetic properties. In this study, Mg–Mg₂Ni–LaH_x nanocomposite is formed from the H-induced decomposition of Mg₉₈Ni_1·67La_0.33 alloy. The hydrogen capacity of 7.19 wt % is reached at 325 °C under 3 MPa H₂, attributed to the ultrahigh hydrogenation capacity in Stage I. The hydrogen capacity of 5.59 wt % is achieved at 175 °C under 1 MPa H₂. The apparent activation energies for hydrogen absorption and desorption are calculated as 57.99 and 107.26 kJ/mol, which are owing to the modified microstructure with LaH_x and Mg₂Ni nanophases embedding in eutectic, and tubular nanostructure adjacent to eutectic. The LaH_2.49 nanophase can catalyze H₂ molecules to dissociate and H atoms to permeate due to its stronger affinity with H atoms. The interfaces of these nanophases provide preferential nucleation sites and alleviate the “blocking effect” together with tubular nanostructure by providing H atoms diffusion paths after the impingement of MgH₂ colonies. Therefore, the superior hydrogenation properties are achieved because of the rapid absorption process of Stage I. The efficient synthesis of nano-catalysts and corresponding mechanisms for improving hydrogen storage properties have important reference to related researches.     

Performance of BaZrO3/Y2O3 dual-phase refractory applied to TiAl alloy melting

Vacuum induction melting is a potential process for the preparation of TiAl alloys with good homogeneity and low cost. But the crucial problem is a selection of high stability refractory. In this study, a BaZrO₃/Y₂O₃ dual-phase refractory was prepared and its performance for melting TiAl alloys was studied and compared with that of a Y₂O₃ refractory. The results showed the dual-phase refractory consisted of BaZr_1-xY_xO_3-δ and Y₂O₃(ZrO₂), exhibited a thinner interaction layer (30 μm) than the Y₂O₃ refractory (90 μm) after melting the TiAl alloy. Although the TiAl alloys melted in the dual-phase and Y₂O₃ refractory exhibited similar oxygen contamination (<0.1 wt%), the alloy melted in the dual-phase refractory had smaller Y₂O₃ inclusion content and size than that in the Y₂O₃ refractory, indicating that the dual-phase refractory exhibited a better melting performance than the Y₂O₃ refractory. This study provides insights into the process of designing highly stable refractory for melting TiAl alloys.     

Nickel‒cobalt bimetallic catalysts prepared from hydrotalcite-like compounds for dry reforming of methane

Ni–Co/Mg(Al)O alloy catalysts with different Co/Ni molar ratios have been prepared from Ni- and Co-substituted Mg–Al hydrotalcite-like compounds (HTlcs) as precursors and tested for dry reforming of methane. The XRD characterization shows that Ni–Co–Mg–Al HTlcs are decomposed by calcination into Mg(Ni,Co,Al)O solid solution, and by reduction finely dispersed alloy particles are formed. H₂-TPR indicates a strong interaction between nickel/cobalt oxides and magnesia, and the presence of cobalt in Mg(Ni,Co,Al)O enhances the metal-support interaction. STEM-EDX analysis reveals that nickel and cobalt cations are homogeneously distributed in the HTlcs precursor and in the derived solid solution, and by reduction the resulting Ni–Co alloy particles are composition-uniform. The Ni–Co/Mg(Al)O alloy catalysts exhibit relatively high activity and stability at severe conditions, i.e., a medium temperature of 600 °C and a high space velocity of 120000 mL g^?1 h^?1. In comparison to monometallic Ni catalyst, Ni–Co alloying effectively inhibits methane decomposition and coke deposition, leading to a marked enhancement of catalytic stability. From CO₂-TPD and TPSR, it is suggested that alloying Ni with Co favors the CO₂ adsorption/activation and promotes the elimination of carbon species, thus improving the coke resistance. Furthermore, a high and stable activity with low coking is demonstrated at 750 °C. The hydrotalcite-derived Ni–Co/Mg(Al)O catalysts show better catalytic performance than many of the reported Ni–Co catalysts, which can be attributed to the formation of Ni–Co alloy with uniform composition, proper size, and strong metal-support interaction as well as the presence of basic Mg(Al)O as support.     

Trimetallic NiFeCr-LDH/MoS2composites as novel electrocatalyst for OER

The development of efficient and stable oxygen evolution reaction (OER) catalysts is an ongoing challenge. In order to solve the problem of low oxygen evolution efficiency of the current OER catalysts, a novel material was synthesized by the incorporation of NiFeCr-LDH and MoS₂, and its structural and electrochemical properties were also investigated. The introduction of MoS₂ improves the electrochemical performance of NiFeCr-LDH. The polarization curve shows that the potential of composite material is only 1.50 V at a current density of 10 mA cm^?2, which is far superior to commercial precious metal catalysts. In addition, the stability experiment shows that the composite material has excellent stability, and the current density has little change after 500 cycles. Furthermore, we found that some metal ions, such as Ni, Cr and Mo, exist in the form of high valence on the surface of NiFeCr-LDH@MoS₂, which is also conducive to the occurrence of oxygen evolution reaction.     

Development of a H2-permeable Pd60Cu40-based composite membrane using a reverse build-up method

A new reverse build-up method is developed to fabricate an economical H₂-permeable composite membrane. Sputtering and electroplating are used for the formation of a membrane comprised of a 3.7-μm-thick Pd₆₀Cu₄₀ (wt.%) alloy layer and a 13-μm-thick porous Ni support layer, respectively. The H₂-permeation measurements are performed under the flow of a gaseous mixture of H₂ and He at 300–320 °C and 50–100 kPa of H₂ partial pressure. The H₂/He selectivity values exceed 300. The activation energy at 300–320 °C is 10.9 kJ mol⁻¹. The H₂ permeability of the membrane is 1.25 × 10⁻⁸ mol m⁻¹ s⁻¹ Pa^−0.5 at 320 °C after 448 h. The estimated Pd cost of the proposed membrane is approximately 1/8 of the cost for a pure Pd₆₀Cu₄₀ membrane. This study demonstrates that the proposed method allows the facile production of low-cost, Pd-based membranes for H₂ separation.     

Microstructure,wear and corrosion characteristics of multiple-reinforced (SiC–B4C–Al2O3) Al matrix composites produced by liquid metal infiltration

In this study, AA7075 aluminum matrix composites reinforced with the combination of SiC, Al₂O₃, and B₄C particles were fabricated by the liquid metal infiltration method. The effects of the relative ratio of B₄C and Al₂O₃ particles on the microstructural, wear, and corrosion features of the composite samples were analyzed using XRD, light metal microscopy, SEM, EDS, Brinell hardness, ball-on-disc type tribometer, and potentiodynamic polarization devices. It was determined that infiltration occurred more successfully, and homogenously distributed particles with reduced porosity were obtained as the amount of Al₂O₃ increased. Worn surface studies revealed that the specimens were predominantly worn by abrasion and adhesion. The increase in B₄C/Al₂O₃ ratio caused a decrease in the hardness and wear strength, whereas it increased the corrosion resistance.     

Reusable Polyacrylonitrile-Sulfur Extractor of Heavy Metal Ions from Wastewater

Mercury, lead, and cadmium are among the most toxic and carcinogenic heavy metal ions (HMIs), posing serious threats to the sustainability of aquatic ecosystems and public health. There is an urgent need to remove these ions from water by a cheap but green process. Traditional methods have insufficient removal efficiency and reusability. Structurally robust, large surface-area adsorbents functionalized with high-selectivity affinity to HMIs are attractive filter materials. Here, an adsorbent prepared by vulcanization of polyacrylonitrile (PAN), a nitrogen-rich polymer, is reported, giving rise to PAN-S nanoparticles with cyclic π-conjugated backbone and electronic conductivity. PAN-S can be coated on ultra-robust melamine (ML) foam by simple dipping and drying. In agreement with hard/soft acid/base theory, N- and S-containing soft Lewis bases have strong binding to Hg²⁺, Pb²⁺, Cu²⁺, and Cd²⁺, with extraordinary capture efficiency and performance stability. Furthermore, the used filters, when collected and electrochemically biased in a recycling bath, can release the HMIs into the bath and electrodeposit on the counter-electrode as metallic Hg⁰, Pb⁰, Cu⁰, and Cd⁰, and the PAN-S@ML filter can then be reused at least 6 times as new. The electronically conductive PAN-S@ML filter can be fabricated cheaply and holds promise for scale-up applications.