Melting process and melt structure of fly ash/magnesium slag blends for the production of inorganic fibers

Fiber production from inorganic industrial solid wastes is an effective waste management strategy. Because of cost considerations, most enterprises generally use local solid wastes as raw materials to produce fibers. In this study, we explored the feasibility of producing fibers using fly ash and magnesium slag. The results show that the melting temperature of the blends composed of fly ash, magnesium slag, and a small amount of calcined dolomite first decreased and then increased with an increase in acidity coefficient (M_k) from 1.0 to 2.4_. The samples could form a eutectic system in the M_k range of 1.4–1.8, and therefore have a relatively low melting temperature in this M_k range. Fly ash could react with magnesium slag and calcined dolomite to form akermanite, gehlenite-magnesium, and anorthite at temperatures close to the melting temperature; therefore, these crystalline phases were the main reaction products formed in the samples with M_k values lower than 1.80. Anorthite reacted further with some Na-containing and Si-containing spieces to produce labradorite. Thus, the content of anorthite and labradorite rapidly increased and they became the major crystal phases in the blend samples with M_k values greater than 1.80. MAS-NMR spectroscopic analysis revealed that the network structure of the melts depended on the ratio of bridging oxygen to non-bridging oxygen; a high ratio of bridging oxygen to non-bridging oxygen could lead to the formation of a dense network structure in the melt. The blends of fly ash and magnesium slag can be used to produce wool fibers and continuous fibers. In addition, the suitable temperature ranges for the production of both types of fibers were determined. The drawing temperature for continuous fiber production depended on the degree of polymerization and structure of the melt.     

Dealloying corrosion of anodic and nanometric Mg41Nd5 in solid solution-treated Mg-3Nd-1Li-0.2Zn alloy

The microstructure and chemical compositions of the solid solution-treated Mg-3Nd-1Li-0.2Zn alloy were characterized using optical microscope,scanning electron microscope(SEM),transmission electron microscope(TEM),electron probe micro-analyzer(EPMA)and X-ray photoelectron spectroscopy(XPS).The corrosion behaviour of the alloy was investigated via electrochemical polarization,electrochemical impedance spectroscopy(EIS),hydrogen evolution test and scanning Kelvin probe(SKP).The results showed that the microstructure of the as-extruded Mg-3Nd-1Li-0.2Zn alloy contained α-Mg matrix and nanometric second phase Mg41 Nd5.The grain size of the alloy increased significantly with the increase in the heat-treatment duration,whereas the volume fraction of the second phase decreased after the solid solution treatment.The surface film was composed of oxides(Nd2O3,MgO,Li2O and ZnO)and carbonates(MgCO3 and Li2CO3),in addition to Nd.The as-extruded alloy exhibited the best corrosion resistance after an initial soaking of 10 min,whereas the alloy with 4h-solution-treatment possessed the lowest corrosion rate after a longer immersion(1 h).This can be attributed to the formation of Nd-containing oxide film on the alloys and a dense corrosion product layer.The dealloying corrosion of the second phase was related to the anodic Mg41Nd5 with a more negative Volta potential relative to α-Mg phase.The preferential corrosion of Mg41Nd5 is proven by in-situ observation and SEM.The solid solution treatment of Mg-3Nd-1Li-0.2Zn alloy led to a shift in corrosion type from pitting corrosion to uniform corrosion under long-term exposure.     

Integrated experimental and thermodynamic modeling study of phase equilibria in the ‘CuO0.5’-MgO-SiO2 system in equilibrium with liquid Cu metal for characterizing refractory-slag interactions

An integrated experimental and thermodynamic modeling study of the phase equilibria in the ‘CuO_0.5’-MgO-SiO₂ system in equilibrium with liquid Cu metal has been undertaken to better understand the reactions between MgO-based refractories and liquid slag in copper converting and refining processes. New experimental phase equilibria data at 1250–1680 °C were obtained for this system using a high-temperature equilibration of synthetic mixtures with predetermined compositions in silica ampoules or magnesia crucibles, a rapid quenching technique, and electron probe X-ray microanalysis of the equilibrated phase compositions. The system has been shown to contain primary phase fields of cristobalite (SiO₂), tridymite (SiO₂), pyroxene/protoenstatite (MgSiO₃), olivine/forsterite (Mg₂SiO₄), periclase (MgO), and cuprite (Cu₂O). Three regions of 2-liquid immiscibility were found—two in the high-silica range of compositions above the cristobalite primary phase field (close to ‘CuO_0.5’-SiO₂ and MgO–SiO₂ binaries) and one in the low-SiO₂, high-‘CuO_0.5’ compositional region above the periclase and olivine phase fields. The results obtained in this study indicate that silica in high-copper refining slags likely led to olivine and pyroxene phase formation, increased solubility of MgO in liquid slag, and decline in the performance of MgO-based refractories. New experimental data were used in the development of a thermodynamic database describing this pseudo-ternary system.     

Enhanced hydrogen desorption kinetics and cycle durability of amorphous TiMgVNi3-doped MgH2

MgH₂ is considered as a promising hydrogen storage material for on-board applications. In order to improve hydrogen storage properties of MgH₂, the amorphous TiMgVNi₃-doped MgH₂ is prepared by ball milling under hydrogen atmosphere. It is found that the catalytic (Ti,V)H₂ and Mg₂NiH₄ nanoparticles are in situ formed after activation. As a result, the amorphous TiMgVNi₃-doped MgH₂ exhibits enhanced dehydrogenation kinetics (the activation energy for hydrogen desorption is 94.4 kJ mol^?1 H₂) and superior cycle durability (the capacity retention rate is up to 92% after 50 cycles). These results demonstrate that the in situ formation of highly dispersed catalytic nanoparticles from an amorphous phase is an effective pathway to enhance hydrogen storage properties of MgH₂.     

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.     

Formation mechanism of porous reaction-bonded silicon nitride with interconnected pores in the presence of MgO

In porous reaction bonded silicon nitride, whiskers normally grow in globular clusters as the dominant morphology and deteriorate the pore interconnectivity. However, the ceramic microstructure was significantly transformed with the addition of MgO; specifically, the morphology was modified to a combination of matte and hexagonal grains. Microstructural observation along with thermodynamic studies suggest that MgO interfered with the presence and nitridation of SiO_(g). Consequently, rather than being involved in the whiskers’ formation, surface silica instead reacted with volatile MgO to form intermediate products. Through these reactions, whisker formation was blocked, and a porous interconnected structure formed which was confirmed by 3D tomography. After heat-treatment at 1700 °C, β-Si₃N₄ crystallized in a glassy matrix containing magnesium. Resulting samples had an open-pore structure with porosity of 74–84 vol. %, and density of 0.48-0.75 g.cm^?3. Combination of high porosity and pore size of <40 μm led to compressive strengths of 1.1–1.6 MPa.     

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.     

Hydrogen desorption from alloys Mg–Cu(–KCl): Cu catalysis in detail

Effect of chemical composition of Mg-xCu based alloys (x = 9.94–58.00 wt %) modified by KCl upon their hydrogen storage performance was studied. Kinetic curves and pressure-concentration isotherms were measured in the ranges up to 60 bar and 388 °C, respectively. It was observed that desorption rate dc/dt is not significantly influenced by the composition. Unknown Cu-rich phase was detected that has shown a catalytic effect on desorption from a mixture with other phases. Activation energy of hydrogen desorption decreased with increasing x from 180 kJ/mol down to 98 kJ/mol. Average hydride dissociation enthalpy, ΔH, for the lowest plateau was 75 kJ/mol which is equal to literature value for pure Mg. Slightly lover average value, 67 kJ/mol was obtained for the second plateau and ΔH for the third one decreased from 70 kJ/mol for the lowest to 49 kJ/mol for the highest x.     

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.     

One-step electrodeposition synthesis of bisphosphonate loaded magnesium implant:A strategy to modulate drug release for osteoporotic fracture healing

Osteoporotic fracture with increase of aging population became an urgent orthopedic problem.Bisphos-phonates were widely recommended as effective clinical treatment drugs.Combination of biodegradable Mg-based implants and merits of bisphosphonates was suggested for osteoporotic fracture healing.Considering the mild and sustained drug release,a novel one-step electrodeposition synthesis of drug loaded coating was proposed in this study.In comparison to conventional soaking method,encapsu-lated zoledronate coating by one-step electrodeposition method could modulate drug release in first diffusion-controlled and later degradation-controlled manner.The in vitro cell response to zoledronate loaded coating showed enhanced proliferation and osteogenic differentiation of osteoblasts and no sig-nificant inhibition on osteoclasts,which could improve bone-forming and decrease bone resorption due to osteoporosis.