Spark Plasma Sintering of Mg-based Alloys:Microstructure,Mechanical Properties,Corrosion Behavior,and Tribological Performance

Within the past ten years,spark plasma sintering(SPS)has become an increasingly popular process for Mg manufacturing.In the SPS process,interparticle diffusion of compressed particles is rapidly achieved due to the concept of Joule heating.Compared to traditional and additive manufacturing(AM)techniques,SPS gives unique control of the structural and microstructural features of Mg components.By doing so,their mechanical,tribological,and corrosion properties can be tailored.Although great advancements in this field have been made,these pieces of knowledge are scattered and have not been contextualized into a single work.The motivation of this work is to address this scientific gap and to provide a groundwork for understanding the basics of SPS manufacturing for Mg.To do so,the existing body of SPS Mg literature was first surveyed,with a focus on their structural formation and degradation mechanisms.It was found that successful Mg SPS fabrication highly depended on the processing temperature,particle size,and particle crystallinity.The addition of metal and ceramic composites also affected their microstructural features due to the Zener pinning effect.In degradative environments,their performance depends on their structural features and whether they have secondary phased composites.In industrial applications,SPS'd Mg was found to have great potential in biomedical,hydrogen storage,battery,automotive,and recycling sectors.The prospects to advance the field include using Mg as a doping agent for crystallite size refinement and using bulk metallic Mg-based glass powders for amorphous SPS components.Despite these findings,the interactions of multi-composites on the processing-structure-property relationships of SPS Mg is not well understood.In total,this work will provide a useful direction in the SPS field and serve as a milestone for future Mg-based SPS manufacturing.

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.

Impressive strides in amelioration of corrosion behavior of Mg-based alloys through the PEO process combined with surface laser process: A review

The unsatisfactory corrosion properties of Mg-based alloys pose a significant obstacle to their widespread application. Plasma electrolytic oxidation(PEO) is a prevalent and effective coating method that produces a ceramic-like oxide coating on the surface of Mg-based alloys,enhancing their resistance to corrosion. Research has demonstrated that PEO treatment can substantially improve the corrosion performance of alloys based on magnesium in the short term. In an effort to enhance the corrosion resistance of PEO coatings over an extended period of time, researchers have turned their attention to the use of laser processes as both pre-and post-treatments in conjunction with the PEO process. Various laser processes, such as laser shock melting(LSM), laser shock adhesion(LSA), laser shock texturing(LST), and laser shock peening(LSP), have been investigated for their potential to improve PEO coatings on Mg substrates and their alloys. These laser melting processes can homogenize and alter the microstructure of Mg-based alloys while leaving the bulk material unchanged, thereby modifying the substrate surface. However, the porous and rough structure of PEO coatings, with their open and interconnected pore structure, can reduce their long-term corrosion resistance. As such, various laser processes are well-suited for surface modification of these coatings. This study will first examine the PEO process and the various types of laser processes used in this process, before investigating the corrosion behavior of PEO coatings in conjunction with laser pre-and post-treatment processes.

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.

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.

Recent progress in Mg-based alloys as a novel bioabsorbable biomaterials for orthopedic applications

Traditional orthopedic metal implants,such as titanium(Ti),Ti alloys,and cobalt-chromium(Co-Cr)alloys,cannot be degraded in vivo.Fracture patients is must always suffer a second operation to remove the implants.Moreover,stress shielding,or stress protection occurs when traditional orthopedic metal implants are applied in fractures surgery.The mechanical shunt produced by traditional orthopedic metal implants can cause bone loss over time,resulting in decreased bone strength and delayed fracture healing.Biodegradable metals that‘biocorrode’are currently attracting significant interest in the orthopedics field due to their suitability as temporary implants.As one of the biodegradable metals,magnesium(Mg)and Mg alloys have gained interest in the field of medicine due to their low density,excellent biocompatibility,high bioresorbability,and proper mechanical properties.Additionally,Mg ions released from the metal implants can promote osteogenesis and angiogenesis during the degradation process in vivo,which is substantially better for orthopedic fixation than other bioinert metal materials.Therefore,this review focuses on the properties,fabrication,biological functions,and surface modification of Mg-based alloys as novel bioabsorbable biomaterials for orthopedic applications.

Laser additive manufacturing of biodegradable Mg-based alloys for biomedical applications: A review

Metallic implants are widely used in internal fixation of bone fracture in surgical treatment.They are mainly used for providing mechanical support and stability during bone reunion,which usually takes a few months to complete.Conventional implants made of stainless steels,Ti-based alloys and CoCrMo alloys have been widely used for orthopedic reconstruction due to their high strength and high corrosion resistance.Such metallic implants will remain permanently inside the body after implantation,and a second surgery after bone healing is needed because the long-term presence of implant will lead to various problems.An implant removal surgery not only incurs expenditure,but also risk and psychological burden.As a consequence,studies on the development of biodegradable implants,which would degrade and disappear in vivo after bone reunion is completed,have drawn researchers’attention.In this connection,Mg-based alloys have shown great potentials as promising implant materials mainly due to their low density,inherent biocompatibility,biodegradability and mechanical properties close to those of bone.However,the high degradation rate of Mg-based implants in vivo is the biggest hurdle to overcome.Apart from materials selection,a fixation implant is ideally tailor-made in size and shape for an individual case,for best surgical outcomes.Therefore,laser additive manufacturing(LAM),with the advent of sophisticated laser systems and software,is an ideal process to solve these problems.In this paper,we reviewed the progress in LAM of biodegradable Mg-based alloys for biomedical applications.The effect of powder properties and laser processing parameter on the formability and quality was thoroughly discussed.The microstructure,phase constituents and metallurgical defects formed in the LAMed samples were delineated.The mechanical properties,corrosion resistance,biocompatibility and antibacterial properties of the LAMed samples were summarized and compared with samples fabricated by traditional processes.In addition,we have made some suggestions for advancing the knowledge in the LAM of Mg-based alloys for biomedical implants.

Microstructure formation and grain refinement of Mg-based alloys by electromagnetic vibration technique

The microstructure formation and grains refinement of two Mg-based alloys,i.e.AZ31 and AZ91D,were reported using an electromagnetic vibration(EMV) technique.These two alloys were solidified at various vibration frequencies and the microstructures were observed.The average size of grains was quantitatively measured as a function of vibration frequencies. Moreover,the grain size distribution was outlined versus number fraction.A novel model was proposed to account for the microstructure formation and grain refinement when considering the significant difference of the electrical resistivity properties of the solid and the liquid during EMV processing in the semisolid state.The remarkable difference originates uncoupled movement between the mobile solid and the sluggish liquid,which can activate melt flow.The microstructure evolution can be well explained when the fluid flow intensity versus vibration frequency is taken into account.Moreover,the influence of the static magnetic field on texture formation is also considered,which plays an important role at higher vibration frequencies.

A new nano-scale surface marking technique for the deformation analysis of Mg-based alloys

In this work a new nanoscale surface marking technique,namely electron beam damage induced surface marking(EBDISM),is developed and tested for the first time on a fine-grained pure Mg surface.This technique utilizes focused high-energy electron beam of a scanning electron microscope to“burn”dense arrays of nano-scale grid patterns on the sample surface,and it is proved to be very effective for identifying and measuring localised deformation behaviours.However,the surface marking deposited by EBDISM is not permanent and it tends to deteriorate overtime.Cheap,easy to use and versatile,the EBDISM technique has a huge potential for quantitative measurement of strain field and nano-scale deformation analysis.

Laser multi-layer cladding of Mg-based alloys

By laser multi-layer cladding using a pulsed Nd-YAG irradiation the thickness of the cladding zone Mg-based alloys(ZM2 and ZM5) can reach about 1.0 mm.The microstructure of the substrate and the cladding zone was studied using optical microscope, scanning electron microscopy(SEM), X-ray diffractometry(XRD) and micro hardness analysis. It is observed that constituent of ZM5 alloy is δ+Mg 17Al 12, that of ZM2 alloy is α+MgZn+Mg 9Ce. That of cladding layer ZM2 alloy(L-ZM2) is Mg+Mg 2Zn 11+MgCe; while that of the cladding layer ZM5 alloy(L-ZM5) is Mg+Mg 32(Al, Zn) 49. The hardness of the cladding area can be increased to values above HV127. Very fine uniform microstructure and the produced new phases of nanometer/sub-micrometer order were obtained. Now, many repaired Mg-based alloy components have been passed by flying test in outside field.

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.

Recent advances in electrochemical performance of Mg-based electrochemical energy storage materials in supercapacitors:Enhancement and mechanism

The application of Mg-based electrochemical energy storage materials in high performance supercapacitors is an essential step to promote the exploitation and utilization of magnesium resources in the field of energy storage.Unfortunately,the inherent chemical properties of magnesium lead to poor cycling stability and electrochemical reactivity,which seriously limit the application of Mg-based materials in supercapacitors.Herein,in this review,more than 70 research papers published in recent 10 years were collected and analyzed.Some representative research works were selected,and the results of various regulative strategies to improve the electrochemical performance of Mg-based materials were discussed.The effects of various regulative strategies(such as constructing nanostructures,synthesizing composites,defect engineering,and binder-free synthesis,etc.)on the electrochemical performance and their mechanism are demonstrated using spinelstructured MgX_(2)O_(4) and layered structured Mg-X-LDHs as examples.In addition,the application of magnesium oxide and magnesium hydroxide in electrode materials,MXene's solid spacers and hard templates are introduced.Finally,the challenges and outlooks of Mg-based electrochemical energy storage materials in high performance supercapacitors are also discussed.

In-situ deposition of apatite layer to protect Mg-based composite fabricated via laser additive manufacturing

Biodegradable magnesium(Mg) and its alloy show huge potential as temporary bone substitute due to the favorable biocompatibility and mechanical compatibility. However, one issue deserves attention is the too fast degradation. In this work, mesoporous bioglass(MBG)with high pore volume(0.59 cc/g) and huge specific surface area(110.78 m^(2)/g) was synthesized using improved sol-gel method, and introduced into Mg-based composite via laser additive manufacturing. Immersion tests showed that the incorporated MBG served as powerful adsorption sites, which promoted the in-situ deposition of apatite by successively adsorbing Ca2+and HPO42-. Such dense apatite film acted as an efficient protection layer and enhanced the corrosion resistance of Mg matrix, which was proved by the electrochemical impedance spectroscopy measurements. Thereby, Mg based composite showed a significantly decreased degradation rate of 0.31 mm/year. Furthermore,MBG also improved the mechanical properties as well as cell behavior. This work highlighted the advantages of MBG in the fabrication of Mg-based implant with enhanced overall performance for orthopedic application.

Nanostructuring of Mg-Based Hydrogen Storage Materials:Recent Advances for Promoting Key Applications

With the depletion of fossil fuels and global warming,there is an urgent demand to seek green,low-cost,and high-efficiency energy resources.Hydrogen has been considered as a potential candidate to replace fossil fuels,due to its high gravimetric energy density(142 MJ kg^(-1)),high abundance(H_(2)O),and environmentalfriendliness.However,due to its low volume density,effective and safe hydrogen storage techniques are now becoming the bottleneck for the"hydrogen economy".Under such a circumstance,Mg-based hydrogen storage materials garnered tremendous interests due to their high hydrogen storage capacity(~7.6 wt%for MgH_(2)),low cost,and excellent reversibility.However,the high thermodynamic stability(ΔH=-74.7 kJ mol^(-1)H_(2))and sluggish kinetics result in a relatively high desorption temperature(>300℃),which severely restricts widespread applications of MgH_(2).Nano-structuring has been proven to be an effective strategy that can simultaneously enhance the ab/de-sorption thermodynamic and kinetic properties of MgH_(2),possibly meeting the demand for rapid hydrogen desorption,economic viability,and effective thermal management in practical applications.Herein,the fundamental theories,recent advances,and practical applications of the nanostructured Mg-based hydrogen storage materials are discussed.The synthetic strategies are classified into four categories:free-standing nano-sized Mg/MgH_(2)through electrochemical/vapor-transport/ultrasonic methods,nanostructured Mg-based composites via mechanical milling methods,construction of core-shell nano-structured Mg-based composites by chemical reduction approaches,and multi-dimensional nano-sized Mg-based heterostructure by nanoconfinement strategy.Through applying these strategies,near room temperature ab/de-sorption(<100℃)with considerable high capacity(>6 wt%)has been achieved in nano Mg/MgH_(2)systems.Some perspectives on the future research and development of nanostructured hydrogen storage materials are also provided.

Guinier-Preston Zone,Quasicrystal and Long-period Stacking Ordered Structure in Mg-based Alloys,A Review

Both the solid solution and precipitation are mainly strengthening mechanism for the magnesium-based alloys. A great number of alloying elements can be dissolved into the Mg matrix to form the solutes and precipitates.Moreover, the type of precipitates varies with different alloying elements and heat treatments, which makes it quite difficult to understand the formation mechanism of the precipitates in Mg-based alloys in depth. Thus, it is very hard to give a systematical regularity in precipitation process for the Mg-based alloys. This review is mainly focused on the formation and microstructural evolution of the precipitates, as a hot topic for the past few years, including Guinier-Preston Zones, quasicrystals and long-period stacking ordered phases formed in a number of Mg-TM-RE alloy systems, where TM = Al, Zn, Zr and RE = Y,Gd, Hd, Ce and La.

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).

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.

Preparation of Al-based Amorphous/Nanocrystalline Composite Coating on Mg-based Alloys Precipitated by Arc Spraying Process

The Al-based amorphous and nanocrystalline composite coatings with the composition of Al-Ni-Y-Co and Al-Ni-Mm-Fe were prepared on AZ91 Mg-based alloys by high velocity arc spraying technique(HVAS).The structure character of the coatings indicates that coatings contain the mixture of amorphous phases and crystalline and there are both less than 2%porosity.The electrochemical tests of the coatings and the substrate were studied.The coatings show the passivation ability during polarization,but AZ91 Mg-based alloys show little passivation.The corrosion current density of the coatings is lower than that of AZ91 Mg-based alloys.The results show that the coatings have an excellent corrosion resistance for AZ91 Mg-based alloys in 5 wt%NaCl solution.

A homogenous microstructural Mg-based matrix model for orthopedic application with generating uniform and smooth corrosion product layer in Ringer’s solution:Study on biodegradable behavior of Mg-Zn alloys prepared by powder metallurgy as a case

For high corrosion resistance and extensively modified biodegradable Mg-based alloys and composites for bone implants,a new Mgbased matrix model prepared by powder metallurgy is discussed and developed.In this research,Mg-5 wt.%Zn alloys were selected as a case.And they were impacted by hot extrusion and aging treatments to construct microstructure with different characteristics.Their selfforming corrosion product layer in Ringer’s solution,biodegradable behavior and corrosion mechanism were minutely investigated by in vitro degradation,electrochemical corrosion and cytocompatibility.The results demonstrated the extruded Mg-5 wt.%Zn alloy aged for 96 h showed high corrosion resistance,good biocompatibility for L929 and excellent ability of maintaining sample integrity during the immersion.Significantly,the alloy showed fine-grain microstructure and uniform distributed hundred nano-sized second phases,which promoted the formation of the uniform and smooth corrosion product layer at the beginning of immersion.The corrosion product layer was more stable in chloride containing aqueous solution and could be directly formed and repaired quickly,which effectively protected the matrix from further corrosion.In addition,an ideal model of Mg-based matrix for bone tissue engineering was tried to presume and propose by discussing the causal relationship between microstructure and bio-corrosion process.

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.