Synergy of inside doped metals–Outside coated graphene to enhance hydrogen storage in magnesium-based alloys

Grain growth of magnesium(Mg)and its hydride is one of the main reasons for kinetic and capacity degradation during the hydrogen absorption and desorption cycles.To solve this problem,herein we propose a novel method involving synergistic effect of inside embedded metals and outside coated graphene to limit the growth of Mg and its hydride grains.The graphene coated Mg-Y-Al alloys were selected as a model system for demonstrating this positive effect where the Mg_(91)Y_(3)Al_(6)alloy was first prepared by rapidly solidified method and then high-pressure milled with 5 wt%graphene upon 5 MPa hydrogen gas for obtaining in-situ formed YAl_(2)and YH_(3)embedded in the MgH_(2)matrix with graphene shell(denoted as MgH_(2)-Y-Al@GR).In comparison to pure MgH_(2),the obtained MgH_(2)-Y-Al@GR composites deliver much better kinetics and more stable cyclic performance.For instance,the MgH_(2)-Y-Al@GR can release about 6.1 wt%H_(2)within 30 min at 300℃ but pure MgH_(2)only desorbs∼1.5 wt%H_(2).The activation energy for desorption of MgH_(2)-Y-Al@GR samples is calculated to be 75.3±9.1 kJ/mol that is much lower than approximately 160 kJ/mol for pure MgH_(2).Moreover,its capacity retention is promoted from∼57%of pure MgH_(2)to∼84%after 50th cycles without obvious particle agglomeration and grain growth.The synergistic effect of outside graphene coating with inside embedded metals which could provide a huge number of active sites for catalysis as well as inhibit the grain growth of Mg and its hydride is believed to be responsible for these.

A state-of-the-art review on recent advances in the fabrication and characteristics of magnesium-based alloys in biomedical applications

Magnesium(Mg)and its alloys have recently gained increasing attention in the biomedical field as promising biodegradable materials with harmless degradation products.Magnesium-based alloys have a wide range of biomedical applications because of their outstanding biocompatibility and unique mechanical properties.Widespread use of Mg-based biomedical devices eliminates the need for post-healing biomaterial removal surgery and minimizes the negative consequences of the implantation of permanent biomaterials,including stress shielding and undesired metal ion release in the body.This paper provides a literature review on the properties and manufacturing methods of Mgbased alloys for biomedical applications,including orthopedic implants,cardiovascular applications,surgical wires and staplers,and antitumor activities.Each application of Mg-based biomaterials is investigated from a biological perspective,including matching functional properties,biocompatibility,host tissue responses,and anti-microbial strategies,along with potential additive manufacturing technologies for these applications.Finally,an outlook is presented to provide recommendations for Mg-based biomaterials in the future.

Pitting corrosion behavior and corrosion protection performance of cold sprayed double layered noble barrier coating on magnesium-based alloy in chloride containing solutions

Nitrogen processed, cold sprayed commercially pure(CP)-Al coatings on Mg-based alloys mostly lack acceptable hardness, wear resistance and most importantly are highly susceptible to localized corrosion in chloride containing solutions. In this research, commercially pure α-Ti top coating having good pitting potential(~1293 mV_(SCE)), high microhardness(HV_(0.025): 263.03) and low wear rate was applied on a CP-Al coated Mg-based alloy using high pressure cold spray technology. Potentiodynamic polarization(PDP) curves indicated that the probability of transition from metastable pits to the stable pits for cold spayed(CS) Al coating is considerably higher compared to that with the CS Ti top coating(for Ti/Al/Mg system). In addition, CS Ti top coating was in the passivation region in most pH ranges even after 48 h immersion in 3.5 wt% NaCl solution. The stored energy in the CS Ti top coating(as a passive metal) was presumed to be responsible for the easy passivation. Immersion tests indicated no obvious pits formation on the intact CS Ti top coating surface and revealed effective corrosion protection performance of the CS double layered noble barrier coatings on Mg alloys in 3.5 wt% NaCl solution even after 264 h.

INVESTIGATION OF LASER BEAM WELDING PROCESS OF AZ61 MAGNESIUM-BASED ALLOY

Laser welling process of AZ61 magnesium alloys is investigated using a special CO2 laser experimental system. The effect of processing parameters including laser power, welling speed, and protection gas flow at the top and bottom is researched. The results show that an ideal well bead can be formed by choosing the processing parameters properly. An optimized parameter range is obtained by a large number of experiments. Among them, laser power and welling speed are the two main parameters that determine the well width and dimensions. The protect gas flow rate has a slight effect on the well width, but it directly effects the surface color of the well. The test results for typical welds indicate that the microhardness and tensile strength of the well zone are better than that of the base metal A fine-grained well region has been observed and no obvious heat-affected zone is found. The well zone mainly consists of small α-Mg phase, （α ＋ Al12Mg17）, and other eutectic phases. The small grains and the eutectic phases in the joint are believed to play an important role in the increase of the strength of wells for AZ61 magnesium alloys.

Laser welding of AZ61 magnesium-based alloys Laser welding of AZ61 magnesium-based alloys

Laser welding of AZ61 magnesium alloys was carried out using a CO2 laser welding experimental system. The welding properties of AZ61 sheets with different thickness were investigated. The effect of processing parameters including laser power, welding speed and protection gas flow was researched. The results show that laser power and welding speed have large effect on the weld width and joint dimensions. Protection gas flow has relatively slight effect on the weld width. The property test of three typical joints indicates that microhardness and tensile strength in weld zone are higher than that of AZ61 base metal, Joints with good appearance and excellent mechanical properties can be produced using CO2 laser welding method. The microstructure with small grains in weld zone is believed to be respoasible for the excellent mechanical properties of AZ61 joints.

Magnesium-based biomaterials for coordinated tissue repair:A comprehensive overview of design strategies,advantages,and challenges

Magnesium-based biomaterials(MBMs)are one of the most promising materials for tissue engineering due to their unique mechanical properties and excellent functional properties.This review describes the development,advantages,and challenges of MBMs for biomedical applications,especially for tissue repair and regeneration.The history of the use of MBMs from the beginning of the 20th century is traced,and the transformative advances in contemporary applications of MBMs in areas such as orthopedics and cardiovascular surgery are emphasized.The review also provides insight into the signaling pathways affected by MBMs,such as the PI3K/Akt and RANKL/RANK/OPG pathways,which are critical for osteogenesis and angiogenesis.The review advocates that future research should focus on optimizing alloy compositions,surface modification and exploring innovative technologies such as 3D printing to improve the efficacy of MBMs in complex tissue repair.The potential of MBMs to tissue engineering and regenerative medicine is significant,urging further exploration and interdisciplinary collaboration to maximize their therapeutic effects.

An overview of magnesium-based implants in orthopaedics and a prospect of its application in spine fusion

Due to matching biomechanical properties and significant biological activity,Mg-based implants present great potential in orthopedic applications.In recent years,the biocompatibility and therapeutic effect of magnesiumbased implants have been widely investigated in trauma repair.In contrast,the R&D work of Mg-based implants in spinal fusion is still limited.This review firstly introduced the general background for Mg-based implants.Secondly,the mechanical properties and degradation behaviors of Mg and its traditional and novel alloys were reviewed.Then,different surface modification techniques of Mg-based implants were described.Thirdly,this review comprehensively summarized the biological pathways of Mg degradation to promote bone formation in neuro-musculoskeletal circuit,angiogenesis with H-type vessel formation,osteogenesis with osteoblasts activation and chondrocyte ossification as an integrated system.Fourthly,this review followed the translation process of Mg-based implants via updating the preclinical studies in fracture fixation,sports trauma repair and reconstruction,and bone distraction for large bone defect.Furthermore,the pilot clinical studies were involved to demonstrate the reliable clinical safety and satisfactory bioactive effects of Mg-based implants in bone formation.Finally,this review introduced the background of spine fusion surgeryand the challenges of biological matching cage development.At last,this review prospected the translation potential of a hybrid Mg-PEEK spine fusion cage design.

Magnesium-based alloys with adapted interfaces for bone implants and tissue engineering

Magnesium and its alloys are one of the most used materials for bone implants and tissue engineering.They are characterized by numerous advantages such as biodegradability,high biocompatibility and mechanical properties with values close to the human bone.Unfortunately,the implant surface must be adequately tuned,or Mg-based alloys must be alloyed with other chemical elements due to their increased corrosion effect in physiological media.This article reviews the clinical challenges related to bone repair and regeneration,classifying bone defects and presenting some of the most used and modern therapies for bone injuries,such as Ilizarov or Masquelet techniques or stem cell treatments.The implant interface challenges are related to new bone formation and fracture healing,implant degradation and hydrogen release.A detailed analysis of mechanical properties during implant degradation is extensively described based on different literature studies that included in vitro and in vivo tests correlated with material properties’characterization.Mg-based trauma implants such as plates and screws,intramedullary nails,Herbert screws,spine cages,rings for joint treatment and regenerative scaffolds are presented,taking into consideration their manufacturing technology,the implant geometrical dimensions and shape,the type of in vivo or in vitro studies and fracture localization.Modern technologies that modify or adapt the Mg-based implant interfaces are described by presenting the main surface microstructural modifications,physical deposition and chemical conversion coatings.The last part of the article provides some recommendations from a translational perspective,identifies the challenges associated with Mg-based implants and presents some future opportunities.This review outlines the available literature on trauma and regenerative bone implants and describes the main techniques used to control the alloy corrosion rate and the cellular environment of the implant.

Magnesium-based nanocomposites:A review from mechanical,creep and fatigue properties

The addition of nanoscale additions to magnesium(Mg)based alloys can boost mechanical characteristics without noticeably decreasing ductility.Since Mg is the lightest structural material,the Mg-based nanocomposites(NCs)with improved mechanical properties are appealing materials for lightweight structural applications.In contrast to conventional Mg-based composites,the incorporation of nano-sized reinforcing particles noticeably boosts the strength of Mg-based nanocomposites without significantly reducing the formability.The present article reviews Mg-based metal matrix nanocomposites(MMNCs)with metallic and ceramic additions,fabricated via both solid-based(sintering and powder metallurgy)and liquid-based(disintegrated melt deposition)technologies.It also reviews strengthening models and mechanisms that have been proposed to explain the improved mechanical characteristics of Mg-based alloys and nanocomposites.Further,synergistic strengthening mecha-nisms in Mg matrix nanocomposites and the dominant equations for quantitatively predicting mechanical properties are provided.Furthermore,this study offers an overview of the creep and fatigue behavior of Mg-based alloys and nanocomposites using both traditional(uniaxial)and depth-sensing indentation techniques.The potential applications of magnesium-based alloys and nanocomposites are also surveyed.

Research perspective and prospective of additive manufacturing of biodegradable magnesium-based materials

Biodegradable metals such as magnesium(Mg)and its alloys have attracted extensive attention in biomedical research due to their excellent mechanical properties and biodegradability.However,traditional casting,extrusion,and commercial processing have limitations in manufacturing components with a complex shape/structure,and these processes may produce defects such as cavities and gas pores which can degrade the properties and usefulness of the products.Compared to conventional techniques,additive manufacturing(AM)can be used to precisely control the geometry of workpieces made of different Mg-based materials with multiple geometric scales and produce desirable medical products for orthopedics,dentistry,and other fields.However,a detailed and thorough understanding of the raw materials,manufacturing processes,properties,and applications is required to foster the production of commercial Mg-based biomedical components by AM.This review summarizes recent advances and important issues pertaining to AM of Mg-based biomedical products and discusses future development and application trends.

Additive manufacturing of biodegradable magnesium-based materials:Design strategies,properties,and biomedical applications

Magnesium(Mg)-based materials are a new generation of alloys with the exclusive ability to be biodegradable within the human/animal body.In addition to biodegradability,their inherent biocompatibility and similar-to-bone density make Mg-based alloys good candidates for fabricating surgical bioimplants for use in orthopedic and traumatology treatments.To this end,nowadays additive manufacturing(AM)along with three-dimensional(3D)printing represents a promising manufacturing technique as it allows for the integration of bioimplant design and manufacturing processes specific to given applications.Meanwhile,this technique also faces many new challenges associated with the properties of Mg-based alloys,including high chemical reactivity,potential for combustion,and low vaporization temperature.In this review article,various AM processes to fabricate biomedical implants from Mg-based alloys,along with their metallic microstructure,mechanical properties,biodegradability,biocompatibility,and antibacterial properties,as well as various post-AM treatments were critically reviewed.Also,the challenges and issues involved in AM processes from the perspectives of bioimplant design,properties,and applications were identified;the possibilities and potential scope of the Mg-based scaffolds/implants are discussed and highlighted.

Accelerated design of high-performance Mg-Mn-based magnesium alloys based on novel bayesian optimization

Magnesium(Mg),being the lightest structural metal,holds immense potential for widespread applications in various fields.The development of high-performance and cost-effective Mg alloys is crucial to further advancing their commercial utilization.With the rapid advancement of machine learning(ML)technology in recent years,the“data-driven''approach for alloy design has provided new perspectives and opportunities for enhancing the performance of Mg alloys.This paper introduces a novel regression-based Bayesian optimization active learning model(RBOALM)for the development of high-performance Mg-Mn-based wrought alloys.RBOALM employs active learning to automatically explore optimal alloy compositions and process parameters within predefined ranges,facilitating the discovery of superior alloy combinations.This model further integrates pre-established regression models as surrogate functions in Bayesian optimization,significantly enhancing the precision of the design process.Leveraging RBOALM,several new high-performance alloys have been successfully designed and prepared.Notably,after mechanical property testing of the designed alloys,the Mg-2.1Zn-2.0Mn-0.5Sn-0.1Ca alloy demonstrates exceptional mechanical properties,including an ultimate tensile strength of 406 MPa,a yield strength of 287 MPa,and a 23%fracture elongation.Furthermore,the Mg-2.7Mn-0.5Al-0.1Ca alloy exhibits an ultimate tensile strength of 211 MPa,coupled with a remarkable 41%fracture elongation.

Relationship between the unique microstructures and behaviors of high-entropy alloys

High-entropy alloys(HEAs),which were introduced as a pioneering concept in 2004,have captured the keen interest of nu-merous researchers.Entropy,in this context,can be perceived as representing disorder and randomness.By contrast,elemental composi-tions within alloy systems occupy specific structural sites in space,a concept referred to as structure.In accordance with Shannon entropy,structure is analogous to information.Generally,the arrangement of atoms within a material,termed its structure,plays a pivotal role in dictating its properties.In addition to expanding the array of options for alloy composites,HEAs afford ample opportunities for diverse structural designs.The profound influence of distinct structural features on the exceptional behaviors of alloys is underscored by numer-ous examples.These features include remarkably high fracture strength with excellent ductility,antiballistic capability,exceptional radi-ation resistance,and corrosion resistance.In this paper,we delve into various unique material structures and properties while elucidating the intricate relationship between structure and performance.

Effects of friction stir processing and nano-hydroxyapatite on the microstructure,hardness,degradation rate and in-vitro bioactivity of WE43 alloy for biomedical applications

Nowadays,magnesium alloys are emerging in biomedical implants for their similar properties to natural bones.However,the rapid degradation of magnesium alloys in biological media hinders successful implantation.Refinement of microstructure,as well as reinforcement particles can significantly improve the degradation rate.In this work,multi-pass friction stir processing(FSP)was proposed to synthesize WE43/nano-hydroxyapatite(n HA)surface composite,the microstructure,reinforced particle distribution,micro-hardness,corrosion behavior and in-vitro bioactivity were studied.The subsequent FSP passes of WE43 alloy and WE43/n HA composite refined the grain size which was reduced by 94.29%and 95.92%(2.63 and 1.88μm,respectively)compared to base metal after three passes.This resulted in increasing the microhardness by 120%(90.86 HV0.1)and 135%(105.59 HV0.1)for the WE43 and WE43-n HA,respectively.It is found that increasing FSP passes improved the uniform distribution of n HA particles within the composite matrix which led to improved corrosion resistance and less degradation rate.The corrosion rate of the FSPed WE43/n HA composite after three passes was reduced by 38.2%(4.13 mm/year)and the degradation rate was reduced by 69.7%(2.87 mm/y).This is attributed to secondary phase(Mg24Y5and Mg41Nd5)particle fragmentation and redistribution,as well as a homogeneous distribution of n HA.Additionally,the growing Ca-P and Mg(OH)2layer formed on the surface represented a protective layer that reduced the degradation rate.The wettability test revealed a relatively hydrophilic surface with water contact angle of 49.1±2.2°compared to 71.2±2.1°for base metal.Also,biomineralization test showed that apatite layer grew after immersion 7d in simulated body fluid with atomic ratio of Ca/P 1.60 approaching the stoichiometric ratio(1.67)indicating superior bioactivity of FSPed WE43/n HA composite after three passes.These results raise that the grain refinement by FSP and introduction of n HA particles significantly improved the degradation rate and in-vitro bioactivity of WE43 alloy for biomedical applications.

Microstructure and damping properties of LPSO phase dominant Mg-Ni-Y and Mg-Zn-Ni-Y alloys

This work studied the microstructure,mechanical properties and damping properties of Mg_(95.34)Ni_(2)Y_(2.66) and Mg_(95.34)Zn_(1)Ni_(1)Y_(2.66)alloys systematically.The difference in the evolution of the long-period stacked ordered(LPSO)phase in the two alloys during heat treatment was the focus.The morphology of the as-cast Mg_(95.34)Ni_(2)Y_(2.66)presented a disordered network.After heat treatment at 773 K for 2 hours,the eutectic phase was integrated into the matrix,and the LPSO phase maintained the 18R structure.As Zn partially replaced Ni,the crystal grains became rounded in the cast alloy,and lamellar LPSO phases and more solid solution atoms were contained in the matrix after heat treatment of the Mg_(95.34)Zn_(1)Ni_(1)Y_(2.66)alloy.Both Zn and the heat treatment had a significant effect on damping.Obvious dislocation internal friction peaks and grain boundary internal friction peaks were found after temperature-dependent damping of the Mg_(95.34)Ni_(2)Y_(2.66)and Mg_(95.34)Zn_(1)Ni_(1)Y_(2.66)alloys.After heat treatment,the dislocation peak was significantly increased,especially in the alloy Mg_(95.34)Ni_(2)Y_(2).66.The annealed Mg_(95.34)Ni_(2)Y_(2.66)alloy with a rod-shaped LPSO phase exhibited a good damping performance of 0.14 atε=10^(−3),which was due to the difference between the second phase and solid solution atom content.These factors also affected the dynamic modulus of the alloy.The results of this study will help in further development of high-damping magnesium alloys.

High corrosion and wear resistant electroless Ni–P gradient coatings on aviation aluminum alloy parts

A Ni–P alloy gradient coating consisting of multiple electroless Ni–P layers with various phosphorus contents was prepared on the aviation aluminum alloy. Several characterization and electrochemical techniques were used to characterize the different Ni–P coatings’ morphologies, phase structures, elemental compositions, and corrosion protection. The gradient coating showed good adhesion and high corrosion and wear resistance, enabling the application of aluminum alloy in harsh environments. The results showed that the double zinc immersion was vital in obtaining excellent adhesion (81.2 N). The optimal coating was not peeled and shredded even after bending tests with angles higher than 90°and was not corroded visually after 500 h of neutral salt spray test at 35℃. The high corrosion resistance was attributed to the misaligning of these micro defects in the three different nickel alloy layers and the amorphous structure of the high P content in the outer layer. These findings guide the exploration of functional gradient coatings that meet the high application requirement of aluminum alloy parts in complicated and harsh aviation environments.

Alloy design for laser powder bed fusion additive manufacturing:a critical review

Metal additive manufacturing(AM)has been extensively studied in recent decades.Despite the significant progress achieved in manufacturing complex shapes and structures,challenges such as severe cracking when using existing alloys for laser powder bed fusion(L-PBF)AM have persisted.These challenges arise because commercial alloys are primarily designed for conventional casting or forging processes,overlooking the fast cooling rates,steep temperature gradients and multiple thermal cycles of L-PBF.To address this,there is an urgent need to develop novel alloys specifically tailored for L-PBF technologies.This review provides a comprehensive summary of the strategies employed in alloy design for L-PBF.It aims to guide future research on designing novel alloys dedicated to L-PBF instead of adapting existing alloys.The review begins by discussing the features of the L-PBF processes,focusing on rapid solidification and intrinsic heat treatment.Next,the printability of the four main existing alloys(Fe-,Ni-,Al-and Ti-based alloys)is critically assessed,with a comparison of their conventional weldability.It was found that the weldability criteria are not always applicable in estimating printability.Furthermore,the review presents recent advances in alloy development and associated strategies,categorizing them into crack mitigation-oriented,microstructure manipulation-oriented and machine learning-assisted approaches.Lastly,an outlook and suggestions are given to highlight the issues that need to be addressed in future work.

Recent innovations in laser additive manufacturing of titanium alloys

Titanium(Ti)alloys are widely used in high-tech fields like aerospace and biomedical engineering.Laser additive manufacturing(LAM),as an innovative technology,is the key driver for the development of Ti alloys.Despite the significant advancements in LAM of Ti alloys,there remain challenges that need further research and development efforts.To recap the potential of LAM high-performance Ti alloy,this article systematically reviews LAM Ti alloys with up-to-date information on process,materials,and properties.Several feasible solutions to advance LAM Ti alloys are reviewed,including intelligent process parameters optimization,LAM process innovation with auxiliary fields and novel Ti alloys customization for LAM.The auxiliary energy fields(e.g.thermal,acoustic,mechanical deformation and magnetic fields)can affect the melt pool dynamics and solidification behaviour during LAM of Ti alloys,altering microstructures and mechanical performances.Different kinds of novel Ti alloys customized for LAM,like peritecticα-Ti,eutectoid(α+β)-Ti,hybrid(α+β)-Ti,isomorphousβ-Ti and eutecticβ-Ti alloys are reviewed in detail.Furthermore,machine learning in accelerating the LAM process optimization and new materials development is also outlooked.This review summarizes the material properties and performance envelops and benchmarks the research achievements in LAM of Ti alloys.In addition,the perspectives and further trends in LAM of Ti alloys are also highlighted.

Influence of heat treatment on microstructure,mechanical and corrosion behavior of WE43 alloy fabricated by laser-beam powder bed fusion

Magnesium(Mg)alloys are considered to be a new generation of revolutionary medical metals.Laser-beam powder bed fusion(PBF-LB)is suitable for fabricating metal implants withpersonalized and complicated structures.However,the as-built part usually exhibits undesirable microstructure and unsatisfactory performance.In this work,WE43 parts were firstly fabricated by PBF-LB and then subjected to heat treatment.Although a high densification rate of 99.91%was achieved using suitable processes,the as-built parts exhibited anisotropic and layeredmicrostructure with heterogeneously precipitated Nd-rich intermetallic.After heat treatment,fine and nano-scaled Mg24Y5particles were precipitated.Meanwhile,theα-Mg grainsunderwent recrystallization and turned coarsened slightly,which effectively weakened thetexture intensity and reduced the anisotropy.As a consequence,the yield strength and ultimate tensile strength were significantly improved to(250.2±3.5)MPa and(312±3.7)MPa,respectively,while the elongation was still maintained at a high level of 15.2%.Furthermore,the homogenized microstructure reduced the tendency of localized corrosion and favoredthe development of uniform passivation film.Thus,the degradation rate of WE43 parts was decreased by an order of magnitude.Besides,in-vitro cell experiments proved their favorable biocompatibility.

An ionic liquid-assisted strategy for enhanced anticorrosion of low-energy PEO coatings on magnesium–lithium alloy

A low-energy plasma electrolytic oxidation(LePEO)technique is developed to simultaneously improve energy efficiency and anti-corrosion.Ionic liquids(1-butyl-3-methylimidazole tetrafluoroborate(BmimBF_(4)))as sustainable corrosion inhibitors are chosen to investigate the corrosion inhibition behavior of ionic liquid(ILs)during the LePEO process for LA91 magnesium-lithium(Mg-Li)alloy.Results show that the ionic liquid BmimBF_(4)participates in the LePEO coating formation process,causing an increment in coating thickness and surface roughness.The low conductivity of the ionic liquid is responsible for the voltage and breakdown voltage increases during the LePEO with IL process(LePEO-IL).After adding BmimBF_(4),corrosion current density decreases from 1.159×10^(−4)A·cm^(−2)to 8.143×10^(−6)A·cm^(−2).The impedance modulus increases to 1.048×10^(4)Ω·cm^(−2)and neutral salt spray remains intact for 24 h.The superior corrosion resistance of the LePEO coating assisted by ionic liquid could be mainly attributed to its compact and thick barrier layer and physical absorption of ionic liquid.The ionic liquid-assisted LePEO technique provides a promising approach to reducing energy consumption and improving film performance.