Biomedical rare-earth magnesium alloy:Current status and future prospects

Biomedical magnesium(Mg)alloys have garnered significant attention because of their unique biodegradability,favorable biocompatibility,and suitable mechanical properties.The incorporation of rare earth(RE)elements,with their distinct physical and chemical properties,has greatly contributed to enhancing the mechanical performance,degradation behavior,and biological performance of biomedical Mg alloys.Currently,a series of RE-Mg alloys are being designed and investigated for orthopedic implants and cardiovascular stents,achieving substantial and encouraging research progress.In this work,a comprehensive summary of the state-of-the-art in biomedical RE-Mg alloys is provided.The physiological effects and design standards of RE elements in biomedical Mg alloys are discussed.Particularly,the degradation behavior and mechanical properties,including their underlying action are studied in-depth.Furthermore,the preparation techniques and current application status of RE-Mg alloys are reviewed.Finally,we address the ongoing challenges and propose future prospects to guide the development of high-performance biomedical Mg-RE alloys.

The strain rate sensitive and anisotropic behavior of rare-earth magnesium alloy ZEK100 sheet

To overcome the limitation in formability at room temperature,manufacturers have developed magnesium alloys with remarkable properties by adding rare-earth elements.The rare-earth magnesium alloys behave differently from the conventional alloys,especially with respect to their coupled anisotropic and strain rate sensitive behavior.In the current work,such behavior of the rare-earth Mg alloy ZEK100 sheet at room temperature is investigated with the aid of the elastic viscoplastic self-consistent polycrystal plasticity model.Different strain rate sensitivities(SRSs)for various deformation modes are employed by the model to simulate the strain rate sensitive behaviors under different loading directions and loading rates.Good agreement between the experiments and simulations reveals the importance and necessity of using different SRSs for each deformation mode in hexagonal close-packed metals.Furthermore,the relative activities of each deformation mode and the texture evolution during different loadings are discussed.The anisotropic and strain rate sensitive behavior is ascribed to the various operating deformation modes with different SRSs during loading along different directions.

Unloading behaviors of the rare-earth magnesium alloy ZE10 sheet

Due to their low symmetry in crystal structure,low elastic modulus(~45 GPa)and low yielding stress,magnesium(Mg)alloys exhibit strong inelastic behaviors during unloading.As more and more Mg alloys are developed,their unloading behaviors were less investigated,especially for rare-earth(RE)Mg alloys.In the current work,the unloading behaviors of the RE Mg alloy ZE10 sheet is carefully studied by both mechanical tests and crystal plasticity modeling.In terms of the stress-strain curves,the inelastic strain,the chord modulus,and the active deformation mechanisms,the substantial anisotropy and the loading path dependency of the unloading behaviors of ZE10 sheets are characterized.The inelastic strains are generally larger under compressive Loading-Un Loading(L-UL)than under tensile L-UL,along the transverse direction(TD)than along the rolling direction(RD)under tensile L-UL,and along RD than along TD under compressive L-UL.The basal slip,twinning and de-twinning are found to be responsible for the unloading behaviors of ZE10 sheets.

Microstructure and mechanical properties of a cast heat-resistant rare-earth magnesium alloy

Microstructure,mechanical properties and phase transformation of a heat-resistant rare-earth(RE)Mg-16.1Gd-3.5Nd-0.38Zn-0.26Zr-0.15Y(wt.%)alloy were investigated.The as-cast alloy is composed of equiaxedα-Mg matrix,net-shaped Mg5RE and Zr-rich phases.According to aging hardening curves and tensile properties variation,the optimized condition of solution treatment at 520℃for 8 h and subsequent aging at 204℃for 12 h was selected.The continuous secondary Mg5RE phase predominantly formed at grain boundaries during solidification transforms to residual discontinuousβ-Mg5RE phase and fine cuboid REH2particles after heat treatment.The annealed alloy exhibits good comprehensive tensile property at 350℃,with ultimate tensile strength of 153 MPa and elongation to fracture of 6.9%.Segregation of RE elements and eventually RE-rich precipitation at grain boundaries are responsible for the high strength at elevated temperature.

Implementation of Balanced Strength and Toughness of VW93A Rare-Earth Magnesium Alloy with Regulating the Overlapping Structure of Lamellar LPSO Phase and β′Phase

Although extensive research has been conducted on the strengthening mechanism of rare-earth magnesium alloys,achieving a balance between strength and toughness has proven challenging.This paper introduces a method for regulating the overlapping structure of the lamellar long-period stacking ordered(LPSO)phase andβ′phase to achieve a balance between strength and toughness in the alloy.By focusing on the extruded VW93A alloy cabin component,the study delves into the mechanism of the alloy's strength and toughness through a comparative analysis of the microstructure characteristics and room-temperature mechanical properties of the alloys in various states.Additionally,the molecular dynamics simulation is employed to clarify the mechanism of the alloy's strength and toughness balance induced by the overlapping structure.The findings reveal that when theβ′phase precipitates in the alloy alone,a significant increase in strength is achieved by pinning dislocations,albeit at the expense of reduced plasticity.Conversely,the presence of the lamellar LPSO phase disperses dislocations between the LPSO phase lamellae,thereby enhancing plasticity by avoiding stress concentration resulting from dislocation stacking.When both phases coexist in the alloy and form an overlapping structure,the dispersion of dislocations due to the lamellar LPSO phase weakens the pinning effect of theβ′phase,further reducing dislocation stacking and resulting in a balance of strength and toughness in the alloy.Ultimately,the alloy with the overlapping structure exhibits an ultimate tensile strength and elongation of 421 MPa and 20.1%,respectively.

Study on the hydrogen absorption properties of a YGdTbDyHo rare-earth high-entropy alloy

This study investigated the microstructure and hydrogen absorption properties of a rare-earth high-entropy alloy(HEA),YGdTbDyHo.Results indicated that the YGdTbDyHo alloy had a microstructure of equiaxed grains,with the alloy elements distributed homogeneously.Upon hydrogen absorption,the phase structure of the HEA changed from a solid solution with an hexagonal-close-packed(HCP)structure to a high-entropy hydride with an faced-centered-cubic(FCC)structure without any secondary phase precipitated.The alloy demonstrated a maximum hydrogen storage capacity of 2.33 H/M(hydrogen atom/metal atom)at 723 K,with an enthalpy change(ΔH)of-141.09 kJ·mol^(-1)and an entropy change(ΔS)of-119.14 J·mol^(-1)·K^(-1).The kinetic mechanism of hydrogen absorption was hydride nucleation and growth,with an apparent activation energy(E_(a))of 20.90 kJ·mol^(-1).Without any activation,the YGdTbDyHo alloy could absorb hydrogen quickly(180 s at 923 K)with nearly no incubation period observed.The reason for the obtained value of 2.33 H/M was that the hydrogen atoms occupied both tetrahedral and octahedral interstices.These results demonstrate the potential application of HEAs as a high-capacity hydrogen storage material with a large H/M ratio,which can be used in the deuterium storage field.

Preparation and performance of coating on rare-earth compounds-immersed magnesium alloy by micro-arc oxidation

A composite ceramic coating containing Y2O3-ZrO2-MgO（YSZ-MgO） was prepared on AZ91D magnesium alloy,which was immersed in Y（NO3）3 aqueous solution as pretreatment,by micro-arc oxidation（MAO） process.The morphology,elemental and phase compositions,corrosion behavior and thermal stability of the coatings were studied by SEM,EDX,XRD,electrochemical corrosion test,high temperature oxidation and thermal shock test.The results show that the coating mainly consists of ZrO2,Y2O3,MgO,Mg2SiO4,and MgF2.Among these compounds,Y2O3 accounts for 26.7% of（Y2O3 ＋ ZrO2）.The thickness of YSZ-MgO coating is smaller than that of ZrO2-MgO coating,but its compactness and surface roughness are better than those of ZrO2-MgO coating.YSZ-MgO coating has a good corrosion resistance,and its corrosion rate in 5% NaCl aqueous solution is lower than that of ZrO2-MgO and only about 8.5% of that of AZ91D magnesium alloy.After oxidation at 410 °C,the mass gain of AZ91D magnesium alloy presents a linear increase with the oxidation time.The YSZ-MgO coating and ZrO2-MgO coating can remarkably decrease the oxidation mass gain.The oxidation mass gain of YSZ-MgO coating is lower than that of ZrO2-MgO coating,especially during a long oxidation period.The thermal shock resistance of YSZ-MgO coating is superior to ZrO2-MgO coating.

Influence of layer thickness on formation quality,microstructure,mechanical properties,and corrosion resistance of WE43 magnesium alloy fabricated by laser powder bed fusion

Laser powder bed fusion(L-PBF)of Mg alloys has provided tremendous opportunities for customized production of aeronautical and medical parts.Layer thickness(LT)is of great significance to the L-PBF process but has not been studied for Mg alloys.In this study,WE43 Mg alloy bulk cubes,porous scaffolds,and thin walls with layer thicknesses of 10,20,30,and 40μm were fabricated.The required laser energy input increased with increasing layer thickness and was different for the bulk cubes and porous scaffolds.Porosity tended to occur at the connection joints in porous scaffolds for LT40 and could be eliminated by reducing the laser energy input.For thin wall parts,a large overhang angle or a small wall thickness resulted in porosity when a large layer thicknesses was used,and the porosity disappeared by reducing the layer thickness or laser energy input.A deeper keyhole penetration was found in all occasions with porosity,explaining the influence of layer thickness,geometrical structure,and laser energy input on the porosity.All the samples achieved a high fusion quality with a relative density of over 99.5%using the optimized laser energy input.The increased layer thickness resulted to more precipitation phases,finer grain sizes and decreased grain texture.With the similar high fusion quality,the tensile strength and elongation of bulk samples were significantly improved from 257 MPa and 1.41%with the 10μm layer to 287 MPa and 15.12%with the 40μm layer,in accordance with the microstructural change.The effect of layer thickness on the compressive properties of porous scaffolds was limited.However,the corrosion rate of bulk samples accelerated with increasing the layer thickness,mainly attributed to the increased number of precipitation phases.

Well-oriented magnesium hydroxide nanoplatelets coating with high corrosion resistance and osteogenesis on magnesium alloy

Magnesium alloys are nontoxic and promising as orthopedic metallic implants,but preparing a biocompatible Mg(OH)_(2)layer with high corrosion protection ability remains challenging.It is generally believed that the Mg(OH)_(2)layer,especially that formed in a natural condition,cannot provide desirable corrosion resistance in the community of corrosion and protection.Here,several Mg(OH)_(2)coatings were prepared by changing the pH values of sodium hydroxide solutions.These coatings were composed of innumerable nanoplatelets with different orientations and showed distinguished capability in corrosion resistance.The nanoplatelets were well-oriented with their ab-planes parallel to,instead of perpendicular to,the magnesium alloy surface by raising the pH value to 14.0.This specific orientation resulted in the optimal coating showing long-term corrosion protection in both in vitro and in vivo environments and good osteogenic capability.These finds manifest that the environment-friendly Mg(OH)_(2)coating can also provide comparable and better corrosion protection than many traditional chemical conversion films(such as phosphate,and fluoride).

Recent progress in the research on magnesium and magnesium alloy foils:A short review

Magnesium and magnesium alloy foils have great potential for application in battery anodes,electromagnetic shielding,optics and acoustics,and biology because of their excellent specific damping,internal dissipation coefficients,magnetic and electrical conductivities,as well as high theoretical specific capacity.However,magnesium alloys exhibit poor deformation ability due to their hexagonal close-packed crystal structure.Preparing magnesium and magnesium alloy foils with thicknesses of less than 0.1 mm is difficult because of surface oxidation and grain growth at high temperatures or severe anisotropy after cold rolling that leads to cracks.Numerous methods have been applied to prepare magnesium alloy foils.They include warm rolling,cold rolling,accumulative roll bonding,electric plastic rolling,and on-line heating rolling.Defects of magnesium and magnesium alloy foils during preparation,such as edge cracks and breakage,are important factors for consideration.Herein,the current status of the research on magnesium and magnesium alloy foils is summarized from the aspects of foil preparation,defect control,performance characterization,and application prospects.The advantages and disadvantages of different preparation methods and defect(edge cracks and breakage)mechanisms in the preparation of foils are identified.

Achieving high ductility and low in-plane anisotropy in magnesium alloy through a novel texture design strategy

Texture regulation is a prominent method to modify the mechanical properties and anisotropy of magnesium alloy.In this work,the Mg-1Al-0.3Ca-0.5Mn-0.2Gd(wt.%)alloy sheet with TD-tilted and circular texture was fabricated by unidirectional rolling(UR)and multidirectional rolling(MR)method,respectively.Unlike generating a strong in-plane mechanical anisotropy in conventional TD-tilted texture,the novel circular texture sample possessed a weak in-plane yield anisotropy.This can be rationalized by the similar proportion of soft grains with favorable orientation for basalslip and{10.12}tensile twinning during the uniaxial tension of circular-texture sample along different directions.Moreover,compared with the TD-tilted texture,the circular texture improved the elongation to failure both along the rolling direction(RD)and transverse direction(TD).By quasi-in-situ EBSD-assisted slip trace analysis,higher activation of basal slip was observed in the circular-texture sample during RD tension,contributing to its excellent ductility.When loading along the TD,the TD-tilted texture promoted the activation of{10.12}tensile twins significantly,thus providing nucleation sites for cracks and deteriorating the ductility.This research may shed new insights into the development of formable and ductile Mg alloy sheets by texture modification.

Interplay of laser power and pore characteristics in selective laser melting of ZK60 magnesium alloys:A study based on in-situ monitoring and image analysis

This study offers significant insights into the multi-physics phenomena of the SLM process and the subsequent porosity characteristics of ZK60 Magnesium(Mg)alloys.High-speed in-situ monitoring was employed to visualise process signals in real-time,elucidating the dynamics of melt pools and vapour plumes under varying laser power conditions specifically between 40 W and 60 W.Detailed morphological analysis was performed using Scanning-Electron Microscopy(SEM),demonstrating a critical correlation between laser power and pore formation.Lower laser power led to increased pore coverage,whereas a denser structure was observed at higher laser power.This laser power influence on porosity was further confirmed via Optical Microscopy(OM)conducted on both top and cross-sectional surfaces of the samples.An increase in laser power resulted in a decrease in pore coverage and pore size,potentially leading to a denser printed part of Mg alloy.X-ray Computed Tomography(XCT)augmented these findings by providing a 3D volumetric representation of the sample internal structure,revealing an inverse relationship between laser power and overall pore volume.Lower laser power appeared to favour the formation of interconnected pores,while a reduction in interconnected pores and an increase in isolated pores were observed at higher power.The interplay between melt pool size,vapour plume effects,and laser power was found to significantly influence the resulting porosity,indicating a need for effective management of these factors to optimise the SLM process of Mg alloys.

Recent developments and applications on high-performance cast magnesium rare-earth alloys

During the past decades,with the increasing demands in lightweight structural materials,Mg alloys with low density and high performance have been extensively investigated and partly applied in some industries.Especially when rare earth(RE)elements are added as major alloying elements to Mg alloys,the alloy strength and creep resistance are greatly improved,which have promoted several series of Mg-RE alloys.This paper reviews the progress and developments of high-performance Mg-RE alloys in recent years with emphasis on cast alloys.The main contents include the alloy design,melt purification,grain refinement,castability,novel liquid casting and semisolid forming approaches,and the industrial applications or trials made of Mg-RE alloys.The review will provide insights for future developments of new alloys,techniques and applications of Mg alloys.

Development and characteristics of a low rare-earth containing magnesium alloy with high strength-ductility synergy

In this study,we successfully developed a low RE containing Mg-3Y-2Gd-1Nd-0.5Zr(wt%)alloy with high strength-ductility synergy by combined processes of hot extrusion,hot rolling and ageing.This alloy exhibits an excellent strength-ductility balance(UTS of 345±2.0 MPa,TYS of 301±5.0 MPa and EL of 9.2±1.9%),which is better than that of many Mg-RE wrought alloys with higher RE concentration and even comparable to that of 6061 Al wrought alloy.A long-range chain-like structure consisting ofβphase,βH phase,βM phase and zig-zag atomic columns is observed for the first time in the studied alloy.The combined process of hot extrusion and hot rolling boosts the formation of deformed grains and low angle grain boundaries,and makes the deformed grains dominate in the alloy strengthening.Under this circumstance,the following ageing generates a novel heterogeneous structure comprising the long-range chain-like structure with broad interparticle spacing and the spacious precipitate-free zones in the deformed grains,which plays a key role in the concurrent strengthening and toughening of the alloy.The present study demonstrates that the deformed grains with long-range chain-like structures and precipitate-free zones is desirable microstructure for the low RE containing Mg alloys to achieve high strength-ductility synergy.

Magnesium alloys as alternative anode materials for rechargeable magnesium-ion batteries:Review on the alloying phase and reaction mechanisms

Magnesium-ion batteries(MIBs)are promising candidates for lithium-ion batteries because of their abundance,non-toxicity,and favorable electrochemical properties.This review explores the reaction mechanisms and electrochemical characteristics of Mg-alloy anode materials.While Mg metal anodes provide high volumetric capacity and dendrite-free electrodeposition,their practical application is hindered by challenges such as sluggish Mg^(2+)ion diffusion and electrolyte compatibility.Alloy-type anodes that incorporate groups XIII,XIV,and XV elements have the potential to overcome these limitations.We review various Mg alloys,emphasizing their alloying/dealloying reaction mechanisms,their theoretical capacities,and the practical aspects of MIBs.Furthermore,we discuss the influence of the electrolyte composition on the reversibility and efficiency of these alloy anodes.Emphasis is placed on overcoming current limitations through innovative materials and structural engineering.This review concludes with perspectives on future research directions aimed at enhancing the performance and commercial viability of Mg alloy anodes and contributing to the development of high-capacity,safe,and cost-effective energy storage systems.

Research advances of magnesium and magnesium alloys globally in 2023

Magnesium materials have attracted the attention of many researchers,and the related research is expanding.This article summarizes the advance in the research and development of magnesium materials globally in 2023 from bibliometric and scientific perspectives.More than 4680 articles on Mg and its alloys were published and indexed in the Web of Science(WoS)Core Collection database last year.The bibliometric analyses show that the traditional structural Mg alloys,functional Mg materials,and corrosion and protection of Mg alloys are still the main research focus.Therefore,this review paper mainly focuses on the research progress of Mg cast alloys,Mg wrought alloys,bio-magnesium alloys,Mg-based energy storage materials,corrosion and protection of Mg alloys in 2023.In addition,future research directions are proposed based on the challenges and obstacles identified throughout this review.

Comprehensive insights into recent innovations:Magnesium-inclusive high-entropy alloys

This review focuses on thermodynamic and physical parameters,synthesis methods,and reported phases of Magnesium(Mg)containing high-entropy alloys(HEAs).Statistical data of publications concerning Mg-containing HEAs were collected and analyzed.Data on the chemical elements included in Mg-containing HEAs,their theoretical end experimental densities,thermodynamic parameters,physical parameters,fabricated techniques and reported phases were also collected and discussed.On the basis of this information,a new classification for HEAs was proposed.It is also shown that the existing thermodynamic parameters cannot accurately predict the formation of a single phase solid solution for Mg-containing HEAs.The physical parameters of Mg-containing HEAs are within a wide range,and most of the synthesized Mg-containing HEAs have a complex multiphase structure.

Degradation and biocompatibility of one-step electrodeposited magnesium thioctic acid/magnesium hydroxide hybrid coatings on ZE21B alloys for cardiovascular stents

Constructing a functional hybrid coating appears to be a promising strategy for addressing the poor corrosion resistance and insufficient endothelialization of Mg-based stents.Nevertheless,the steps for preparing composite coatings are usually complicated and time-consuming.Herein,a novel composite coating,composed of bioactive magnesium thioctic acid(MTA)layer formed by deposition and corrosion-resistant magnesium hydroxide(Mg(OH)_(2))layer grown in situ,is simply fabricated on ZE21B alloys via one-step electrodeposition.Scanning electron microscopy(SEM)shows that the electrodeposited coating has a compact and uniform structure.And the high adhesion of the MTA/Mg(OH)_(2)hybrid coating is also confirmed by the micro-scratch test.Electrochemical test,scanning kelvin probe(SKP),and hydrogen evolution measurement indicate that the hybrid coating effectively reduces the degradation rate of Mg substrates.Haemocompatibility experiment and cell culture trial detect that the composite coating is of fine biocompatibility.Finally,the preparation mechanism of MTA/Mg(OH)_(2)hybrid coatings is discussed and proposed.This coating shows a great potential application for cardiovascular stents.

Effects of orientation on the fatigue crack growth behaviors of the ZK60 magnesium alloy in air and PBS

Strong anisotropic corrosion and mechanical properties caused by specimen orientations greatly limit the applications of wrought magnesium alloys.To investigate the influences of specimen orientation,the corrosion tests and(corrosion)fatigue crack growth tests were conducted.The rolled and transverse surfaces of the materials show distinct corrosion rate differences in the stable corrosion stage,but the truth is the opposite for the initial stage of corrosion.In air,specimen orientations have a significant influence on the plastic deformation mechanisms near the crack tip,which results in different fatigue fracture surfaces and cracking paths.Compared with R-T specimens,N-T specimens show a slower fatigue crack growth(FCG)rate in air,which can be attributed to crack closure effects and deformation twinning near the crack tip.The corrosion environment will not significantly change the main plastic deformation mechanisms for the same type of specimen.However,the FCG rate in phosphate buffer saline(PBS)is one order of magnitude higher than that in air,which is caused by the combined effects of hydrogen-induced cracking and anodic dissolution.Owing to the similar corrosion rates at crack tips,the specimens with different orientations display close FCG rates in PBS.

The influence of yttrium and manganese additions on the degradation and biocompatibility of magnesium-zinc-based alloys:In vitro and in vivo studies

The repair and regeneration of bone defects are highly challenging orthopedic problems.Recently,Mg-based implants have gained popularity due to their unique biodegradation and elastic modulus similar to that of human bone.The aim of our study is to develop a magnesium alloy with a controllable degradation that can closely match bone tissue to help injuries heal in vivo and avoid cytotoxicity caused by a sudden increase in ion concentration.In this study,we prepared and modified Mg-3Zn,Mg-3Zn-1Y,and Mg-2Zn-1Mn by hot extrusion,and used Mg-2.5Y-2.5Nd was as a control.We then investigated the effect of additions of Y and Mn on alloys'properties.Our results show that Mn and Y can improve not only compression strength but also corrosion resistance.The alloy Mg-2Zn-1Mn demonstrated good cytocompatibility in vitro,and for this reason we selected it for implantation in vivo.The degraded Mg-2Zn-1Mn implanted a bone defect area did not cause obvious rejection and inflammatory reaction,and the degradation products left no signs of damage to the heart,liver,kidney,or brain.Furthermore,we find that Mg-2Zn-1Mn can promote an osteoinductive response in vivo and the formation of bone regeneration.