Progress and prospects of Mg-based amorphous alloys in azo dye wastewater treatment

Mg-based amorphous alloys exhibit efficient catalytic performance and excellent biocompatibility with a promising application probability,specifically in the field of azo dye wastewater degradation.However,the problems like difficulty in preparation and poor cycling stability need to be solved.At present,Mg-based amorphous alloys applied in wastewater degradation are available in powder and ribbon.The amorphous alloy powder fabricated by ball milling has a high specific surface area,and its reactivity is thousands of times better than that of gas atomized alloy powder.But the development is limited due to the high energy consumption,difficult and costly process of powder recycling.The single roller melt-spinning method is a new manufacturing process of amorphous alloy ribbon.Compared to amorphous powder,the specific surface area of amorphous ribbon is relatively lower,therefore,it is necessary to carry out surface modification to enhance it.Dealloying is a way that can form a pore structure on the surface of the amorphous alloys,increasing the specific surface area and providing more reactive sites,which all contribute to the catalytic performance.Exploring the optimal conditions for Mg-based amorphous alloys in wastewater degradation by adjusting amorphous alloy composition,choosing suitable method to preparation and surface modification,reducing cost,expanding the pH range will advance the steps to put Mg-based amorphous alloys in industrial environments into practice.

Hydrogen absorption/desorption cycling performance of Mg-based alloys with in-situ formed Mg_(2)Ni and LaH_(x)(x=2,3)nanocrystallines

Aiming to elucidate the hydrogen absorption/desorption cycling properties of Mg-based alloys with in-situ formed Mg_(2)Ni and LaH_(x)(x=2,3)nanocrystallines,the hydrogen storage cycle stability,hydriding/dehydriding cycling kinetics and thermodynamic stability of the experimental alloys have been investigated in detail.The results show that the Mg-Ni-La alloys exhibit improved hydrogen storage cycling properties and can remain storage hydrogen above 5.5 wt%after 200 cycles.With the increase of cycling numbers,the dehydrogenation rates of the experimental samples increase firstly and then gradually decrease,and eventually maintain relative stable state.Microstructure observation reveals that powders sintering and hydrogen decrepitation both exist during hydrogen absorption/desorption cycles due to repeated volume expansion and contraction.Meanwhile,the in-situ formed LaH_(x)(x=2,3)and Mg_(2)Ni nanocrystallines stabilize the microstructures of the particles and hinder the powders sintering.After 200 cycles,the average particle size of the experimental samples decreases and the specific surface area apparently increases,which leads to the decomposition temperatures of MgH_(2)and Mg_(2)NiH_(4)slightly shift to lower temperatures.Moreover,Mg_(2)Ni and LaH_(x)(x=2,3)have been proven to be stable catalysts during long-term cycling,which can still uniformly distribute within the powders after 200 cycles.

A comprehensive review on biocompatible Mg-based alloys as temporary orthopaedic implants:Current status,challenges,and future prospects

Mg and its alloys are drawing huge attention since the last two decades as a viable option for temporary implants applications.A commendable progress has already been made in the development of these alloys.The biodegradable nature of Mg,appreciable biocompatibility of elemental Mg,and its close resemblance to natural bone in terms of density and elastic modulus make them highly preferable option amongst other available alternatives in this field.This review article presents an overview covering the recent advancements made in the field of Mg-based biodegradable implants for orthopaedic implant applications.The paper focuses on alloy development and fabrication techniques,the state of the art of important Mg-based alloy systems in terms of their mechanical properties,in-vitro and in-vivo degradation behaviour and cytotoxicity.Further,the paper reviews the current progress achieved in the clinical transition of Mg-based alloys for orthopaedic fixtures.The review also includes the degradation mechanisms of the alloys in physiological environment and highlights the mismatch existing between the rate of bone healing and alloy degradation due to rapid corrosion of the alloys in such environment,which has still restricted their widespread application.Finally,the surface coating techniques available for the alloys as an effective way to reduce the degradation rate are reviewed,followed by a discussion on the future research prospects.

Effect of Heat-Treatment Process on Properties of Rare Earth Mg-Based System Hydrogen Storage Alloys with AB_3-Type

The effect of heat-treatment process on the properties of Mm0.8Mg0.2(NiCoAlMn)3.5 hydrogen storage alloy was discussed . The electrochemical properties such as cycling stability, activation property, and the plateau voltage of the alloy which was heat-treated in various temperatures and times had different changes during the cycle process, the optimum heat-treatment conditions of this alloy were determined by this work.

Study on Nanocrystalline Rare Earth Mg-Based System Hydrogen Storage Alloys with AB_3-Type

A sort of rare earth Mg-based system hydrogen storage alloys with AB3-type was prepared by double-roller rapid quenching method. The alloys were nanocrystalline multi-phase structures composed of LaNi3 phase and LaNi5 phase by X-ray diffraction and scanning electron microscopy analyses, and the suitable absorption/desorption plateau was revealed by the measurement of P-C-I curve. Electrochemical studies indicate that the alloys exhibit good electrochemical properties such as high capacity and stable cycle life, and the discharge capacity is 369 mAh·g-1 at 0.2 C (72 mA·g-1). after 460 cycles, the capacity decay was only 19.4% at 2 C (720 mA·g-1).

Hydrogen storage behavior of Mg-based alloy catalyzed by carbon-cobalt composites

The composites comprised of Co nanoparticle and C nanosheet were prepared though a high-temperature carbonization reaction.The catalysis of Co@C composites on the hydrogen storage behavior of Mg_(90)Ce_(5)Y_(5)alloy was investigated in detail by XRD,SEM,TEM,PCI,and DSC method.Because of the synergistic catalytic function of C and Co in C@Co nanocomposites,the Mg_(90)Ce_(5)Y_(5)alloy with 10 wt.%C@Co shows the excellent hydrogen absorption and desorption performances.Time for releasing hydrogen reduces from 150 min to 11 min with the addition of the C@Co composites at the temperature of 300℃.Meanwhile,the dehydrogenation activation energy also declines from 130.3 to 81.9 kJ mol^(-1)H_(2)after the addition of the C@Co composites.This positive effect attributes to the C layer with the high defect density and the Co nanoparticles,which reduces the energy barriers for the nucleation of Mg/MgH_(2)phase and the recombination of hydrogen molecule.Besides,the C@Co composites also improve the activation property of the Mg_(90)Ce_(5)Y_(5)alloy which was folly activated in the first cycle.Moreover,the temperature for initial dehydrogenation and the endothermic peak of the alloy hydride were also decreased.Although the addition of the C@Co composites increases the plateau pressures and decreases the value of the decomposition enthalpy,these differences are so small that the improvement on thermodynamics can hardly be seen.

Thermal stability of nanocrystalline Mg-based alloys prepared via mechanical alloying

Thethermal stability and the kinetics of grain growth of nanocrystalline Mg-6Al-1Zn and Mg-6Al-1Zn-1Si alloys prepared via mechanical alloying were investigated. It started with elemental powders, using a variety of analytical techniques including differential scanning calorimetry （DSC）, X-ray diffraction （XRD）, scanning electron microscopy （SEM）, transmission electron microscopy （TEM） and energy dispersive spectrometry. The kinetics of grain growth in isothermal annealing was investigated. The XRD results show that, although the grain sizes of both material systems increase as the annealing temperature rises, the Si-containing system displays a relatively smaller grain size, i.e., 60 nm compared with 72 nm in Mg-6Al-1Zn system, after being exposed to 350 ℃ for 1 h. The second-phase intermetallic particle Mg2Si formed during the isothermal annealing of Mg-6Al-1Zn-1Si system could influence not only the activation energy but also the exponent of kinetic equation. Higher hardness values obtained in the Si-containing system would be due to the formation of Mg2Si intermetallic phase.

Thermodynamic modeling of the La-Mg-Y system and Mg-based alloys database

As an example of the La-Mg-Y system, the method how to set up the themaodynamic model of individual phases was introduced in the process of thermodynamic optimization. The solution phases （liquid, body-centered cubic, face-centered cubic, hexagonal close-packed and double hexagonal close-packed） were modeled with the Redlich-Kister equation. The compound energy model has been used to describe the thermodynamic functions of the intermetallic compounds in the La-Mg-Y systems. The compounds Mg2Y, Mg24Y5, Mg12La, Mg17La2, Mg41Las, Mg3La and Mg2La in the La-Mg-Y system were treated as the formulae （Mg,Y）2（La,Mg,Y）, Mg24（La,Mg,Y）4Y, Mg12（La, Y）, Mg17（La,Y）2, Mg41（La,Y）5, Mg3（La,Mg,Y） and Mg2（La, Y）, respectively. A model （La, Mg,Y）0.5（La,Mg,Y）0.5 was applied to describe the compound MgM formed by MgLa and MgY in order to cope with the order-disorder transition between body-centered cubic solution （A2） and MgM with CsCl-type structure （B2） in the La-Mg-Y system. The Gibbs energies of individual phases were optimized in the La-Mg, La-Y and La-Mg-Y systems by CALPHAD technique. The projection of the liquidus surfaces for the La-Mg-Y system was predicted. The Mg-based alloys database including 36 binary and 15 ternary systems formed by Mg, Al, Cu, Ni, Mn, Zn and rare earth elements was set up in SGTE standard.

Development of Mg-based Hydrogen Storage Alloy

Mg-based hydrogen storage alloys are considered as a promising candidate for hydrogen system because of its lightweight, high storage capacity, low price and rich mineral resources. In detail, we reviewed the preparation and properties of Mg-Ni-based hydrogen storage alloys. All kinds of attempts have been done to improve the hydriding and dehydriding behaviors. It is found that the partial substitution of foreign elements can decrease the hydrogen absorption temperature, especially the substitution of a more electronegative element, such as AI and Mn. Mechanical alloying (MA) and mechanical grinding (MG) are the most effective methods to improve the hydriding/dehydriding kinetics and electrochemical capacity, and decrease the desorption temperature. but the corrosion resistance is so poor that the 80% of maximum capacity is lost within ten cycles. Microencapsulation is a useful measurement for improving the corrosion resistance and electrocatalytic activity. fn order to improve the properties of the alloys for practical application, the alloys should have a large number of defects, which give activated sites, subsequently, MA, MG and electroless plating should be used to improve the hydriding/dehydriding kinetics and protect the surface of alloys, respectively. The new composite Mg-based alloys give a new way for the hydrogen storage material to practical application. Furthermore we put forward several problems which will be discussed in future.

Shell and shrinking core kinetics model of Mg-based hydrogen storage alloys

The kinetics equation of the Mg-based hydrogen storage alloys (Mg-Ni-MO) was established by the shell and shrinking core model. The total coefficients of the kinetics equation of the hydrogen absorption and desorption process with shell diffusion as the controlling step were determined by semi-empirical and semi-theoretical methods, and the apparent activation energy of the hydrogen absorption process was obtained. The calculation results can well accord with the experimental data, and can well forecast the hydrogen storage capacity and absorption rate at different times. By using the kinetics equation, the effects of temperature and pressure on the hydrogen storage process can also be well understood. The kinetics equation is helpful for the design of the hydrogen storage container.

Recent Progress on Electrode Characteristics of Mg and Mg-Based Hydrogen Storage Alloys

Recent development of Mg and Mg-based hydrogen storage alloys used in Ni-MH battery was discussed extensively. The results obtained from recent studies prove that these alloys with nanocrystalline/amorphous structure formed by mechanical alloying (MA) or mechanical grinding (MG) have good electrode characteristics. In general, MA or MG, and elemental substitution alloying are regarded as the effective means to seek new system of Mg-based alloys and nano-composite with improved electrode characteristics. However, until now, the currently known improvement in these electrode characteristics is still far from reach to that required for commercial application.

Effects of doping Fe and Al on microstructure and electrochemical characteristics of Mg-based hydrogen storage alloys

The Mg-based hydrogen storage alloys Mg2Ni, Mg2Ni0.7Fe0.3 and Mgl.7Alo.3Ni were successfully synthesized by a two-step process （sintering and ball milling）. The crystal structure and microstructure were examined by X-ray diffraction, Scanning Electron Microscope and Malvern particle size analyzer. New phase appears in the tripe alloys doped with A1 and Fe, and the particle size ranges from 3μm to 5 μm. The electrochemical performance studies indicate that the partial substitution of AI for Mg, and Fe for Ni significantly improve the cycle life, reversibility of hydrogen absorption and desorption. The diffusion process is the control step in the electrode reaction of hydrogen storage alloys.

An overview of progress in Mg-based hydrogen storage films

Mg-based hydrogen storage materials are considered to be one of the most promising solid-state hydrogen storage materials due to their large hydrogen storage capacity and low cost. However, slow hydrogen absorption/desorption rate and excessive hydrogen absorption/desorption temperature limit the application of Mg-based hydrogen storage materials.The present paper reviews the advances in the research of Mg-based hydrogen storage film in recent years, including the advantage of the film, the function theory of fabricating method and its functional theory, and the influencing factors in the technological process. The research status worldwide is introduced in detail. By comparing pure Mg, Pd-caped Mg, nonpalladium capped Mg, and Mg alloy hydrogen storage films, an ideal tendency for producing Mg-based film is pointed out,for example, looking for a cheap metal element to replace the high-priced Pd, compositing Mg film with other hydrogen storage alloy of catalytic elements, and so on.

Research advances of magnesium and magnesium alloys worldwide in 2022

More than 4600 papers in the field of Mg and Mg alloys were published and indexed in the Web of Science(WoS)Core Collection database in 2022.The bibliometric analyses indicate that the microstructure,mechanical properties,and corrosion of Mg alloys are still the main research focus.Bio-Mg materials,Mg ion batteries and hydrogen storage Mg materials have attracted much attention.Notable contributions to the research and development of magnesium alloys were made by Chongqing University(>200 papers),Chinese Academy of Sciences,Shanghai Jiao Tong University,and Northeastern University(>100 papers)in China,Helmholtz Zentrum Hereon in Germany,Ohio State University in the USA,the University of Queensland in Australia,Kumanto University in Japan,and Seoul National University in Korea,University of Tehran in Iran,and National University of Singapore in Singapore,etc.This review is aimed to summarize the progress in the development of structural and functional Mg and Mg alloys in 2022.Based on the issues and challenges identified here,some future research directions are suggested.

Crystallization microstructure of Mg_(65)Cu_(25)Y_(10) bulk amorphous alloy

Mg65Cu25Y10 bulk amorphous alloy specimens prepared by conventional copper mould method were heated at 200 °C for different time and the phase contents as well as microstructure were studied.The XRD results show that the crystallization of Mg65Cu25Y10 bulk amorphous alloy specimen becomes complete as the treating time increases and Mg2Cu,Mg24Y5 and HCP-Mg crystalline phases are found.Snowflake-like morphology is found in different specimens through SEM observation.The EDS patterns show that the composition of the snowflake-like structure is close to that of the as-cast alloy.Laminated structures are observed from the TEM images of the snowflake-like structure.From the electron diffraction patterns,it is seen that the snowflake-like structure is the combination of Mg24Y5 and amorphous matrix.The FCC-Mg phase in the matrix transforms into HCP-Mg during the heat-treating process.

Microstructural evolution of melt-spun Mg-10Ni-2Mm hydrogen storage alloy

The microstructural evolution of a Mg-10Ni-2Mm（molar fraction,%）（Mm=Ce,La-rich mischmetal） hydrogen storage alloys applied with various solidification rates was studied.The results show that the grain size of melt-spun ribbon is remarkably reduced by increasing the solidification rate.The microcrystalline,nanocrystalline and amorphous microstructures are obtained by applying the surface velocities of the graphite wheel of 3.1,10.5 and 20.9 m/s,respectively.By applying the surface velocity of the graphite wheel of 3.1 m/s,the melt-spun specimen obtains full crystalline with a considerable amount of coarse microcrystalline Mg and Mg2Ni except for some Mm-rich particles.The amount of nanocrystalline phases significantly increases with increasing the surface velocity of the wheel to 10.5 m/s,and the microstructure is composed of a large amount of nanocrystalline phases of Mg and Mg2Ni particles.A mixed microstructure containing amorphous and nanocrystalline phases is obtained at a surface velocity of the wheel of 20.9 m/s.The optimal microstructure with a considerable amount of nanocrystalline Mg and Mg2Ni in an amorphous matrix is expected to have the maximum hydrogen absorption capacity and excellent hydrogenation kinetics.

Effect of addition of Si on microstructure, mechanical properties, bio-corrosion and cytotoxicity of Mg-6Al-1Zn alloy

The Mg-6Al-4Zn alloy was fabricated by mechanical alloying(MA)and hot pressing to serve as biodegradable metal implant.The influence of addition of 1%Si(mass fraction)on the microstructure,mechanical properties and bio-corrosion behavior of Mg-6Al-1Zn alloy was studied using X-ray diffractometry,transmission electron microscopy,compression test,as well as immersion,electrochemical test and MTT assay.The results showed that the addition of 1%Si to Mg-6Al-1Zn alloy led to the formation of fine Mg2Si phase with polygonal shape,and increased compressive strength,elongation and improved corrosion resistance.Furthermore,the cell viability of Saos-2 cells has been improved by addition of 1%Si to Mg-6Al-1Zn alloy.According to the results,the magnesium ions released in the methylthiazol tetrazolium(MTT)test have not shown any cell toxicity.All these indicated that the addition of 1%Si improved the properties of Mg-6Al-4Zn alloy for using as a biodegradable implant.

Glass-forming ability and crystallization of Mg-Ni amorphous alloys with Y addition

Mg86.33Ni13.67-xYx(x=0, 1, 3, 6, 10) amorphous alloys were obtained by single-roller melt-spinning technique and the effect of Y addition on the glass forming ability(GFA), crystallization and micro-hardness of Mg-Ni alloys were studied. The results show that the GFA of Mg86.33Ni13.67-xYx(x=0, 1, 3, 6, 10) is improved successfully with the Y addition. The highest GFA appeares at x=6, while the reduced glass transition temperature (Trg) is 0.5225 and the supercooled liquid region(ΔTx) is 42.06 K; the position of the main diffraction halo is different for the alloys, and the maximum of the main diffraction halo of alloys with x=0, 1, 3 corresponds to the main peaks of a metastable fcc-Mg6Ni or fcc-Mg6Ni + Ni-Y intermetallic phases, and for the alloys with x=6, 10, it corresponds to Mg-Y and Ni-Y intermetallic phases; the micro-hardness of the alloys is improved with Y additions, and the highest micro-hardness is obtained at x=6 at.%, which is 960 MPa.

Microstructure, hydrogen storage thermodynamics and kinetics of La_5Mg_(95-x)Ni_x(x=5, 10, 15) alloys

The microstructure, hydrogen storage thermodynamics and kinetics of La5Mg95-xNix (x=5, 10, 15) ternary alloys with different Ni contents were investigated. The evolutions of the microstructure and phase of experimental alloys were characterized by X-ray diffractometry and scanning electron microscopy. The hydrogen storage kinetics and thermodynamics, and P-C-I curves were tested using a Sievert apparatus. It is found that increasing Ni content remarkably improves hydrogen storage kinetics but reduces the hydrogen storage capacity of alloys. The highest hydrogen absorption/desorption rate is observed in the La5Mg80Ni15 alloy, with the lowest hydrogen desorption activation value being 57.7 kJ/mol. By means of P-C-I curves and the van’t Hoff equation, it is determined that the thermodynamic performance of the alloy is initially improved and then degraded with increasing Ni content. The La5Mg85Ni10 alloy has the best thermodynamics properties with a hydrogenation enthalpy of -72.1 kJ/mol and hydrogenation entropy of -123.2 J/(mol·K).

Corrosion and discharge behavior of Mg−xLa alloys(x=0.0−0.8) as anode materials

The corrosion and discharge performances of binary Mg−xLa(x=0.2−0.8,wt.%)alloys as anode materials for Mg-based batteries were evaluated.Microstructure,hydrogen evolution,mass loss,electrochemical behavior,and half-cell discharge capabilities were characterized.The results show that the corrosion rate of the Mg matrix was decreased by alloying with La,and this could be attributed to the formation of a protective La2O3-containing film on the surface of the alloy.The Mg−0.2La alloy displayed the lowest corrosion rate,i.e.,2.4 mm/a in a 3.5 wt.%NaCl solution,Furthermore,the discharge performance of Mg−0.4La alloy was superior to that of pure Mg and other Mg−La alloys;this could be associated with the modified microstructure of the Mg−0.4La alloy,which decreased the self-corrosion and accelerated the detachment of the discharge products.