In vivo and in vitro study of resorbable magnesium wires for medical implants:Mg purity,surface quality,Zn alloying and polymer coating

Magnesium is an excellent material in terms of biocompatibility and its corrosion products can serve as an active source for new bone formation.However,localized corrosion and H_(2)generation limit the potential of Mg-based implants.Utilizing low-alloyed Mg-Zn wires can strongly reduce problems with large H_(2)bubbles and improve the mechanical properties considerably while maintaining excellent long-term biocompatibility.Acidic pickling and a polymer coating can be effectively used to lower the rate of in vivo degradation.In this work,microstructural,mechanical,and in vitro characterization of 250μm and 300μm extruded wires made from ultra-pure Mg,commercially pure Mg,Mg-0.15Zn,Mg-0.4Zn and Mg-1Zn was performed.Additionally,Mg-0.4Zn wires together with a variant coated with a copolymer of L-lactide andε-caprolactone were tested in vivo on artificially damaged Wistar rat femurs.Based on the observed Mg-induced osteogenesis,polymer-coated Mg wires with a small addition of Zn are a perspective material for bone-support applications,such as cerclage and fixation wires.

High formability Mg-Zn-Gd wire facilitates ACL reconstruction via its swift degradation to accelerate intra-tunnel endochondral ossification

After reconstructing the anterior cruciate ligament(ACL),unsatisfactory bone tendon interface healing may often induce tunnel enlargement at the early healing stage.With good biological features and high formability,Magnesium-Zinc-Gadolinium(ZG21)wires are developed to bunch the tendon graft for matching the bone tunnel during transplantation.Microstructure,tensile strength,degradation,and cytotoxicity of ZG21 wire are evaluated.The rabbit model is used for assessing the biological effects of ZG21 wire by Micro-CT,histology,and mechanical test.The SEM/EDS,immunochemistry,and in vitro assessments are performed to investigate the underlying mechanism.Material tests demonstrate the high formability of ZG21 wire as surgical suture.Micro-CT shows ZG21 wire degradation accelerates tunnel bone formation,and histologically with earlier and more fibrocartilage regeneration at the healing interface.The mechanical test shows higher ultimate load in the ZG21 group.The SEM/EDS presents ZG21 wire degradation triggered calcium phosphate(Ca-P)deposition.IHC results demonstrate upregulation of Wnt3a,BMP2,and VEGF at the early phase and TGFβ3 and Type II collagen at the late phase of healing.In vitro tests also confirmed the Ca-P in the metal extract could elevate the expression of Wnt3a,βcatenin,ocn and opn to stimulate osteogenesis.Ex vivo tests of clinical samples indicated suturing with ZG21 wire did not weaken the ultimate loading of human tendon tissue.In conclusion,the ZG21 wire is feasible for tendon graft bunching.Its degradation products accelerated intra-tunnel endochondral ossification at the early healing stage and therefore enhanced bone-tendon interface healing in ACL reconstruction.

Customized heat treatment process enabled excellent mechanical properties in wire arc additively manufactured Mg-RE-Zn-Zr alloys

Customized heat treatment is essential for enhancing the mechanical properties of additively manufactured metallic materials,especially for alloys with complex phase constituents and heterogenous microstructure.However,the interrelated evolutions of different microstructure features make it difficult to establish optimal heat treatment processes.Herein,we proposed a method for customized heat treatment process exploration and establishment to overcome this challenge for such kind of alloys,and a wire arc additively manufactured(WAAM)Mg-Gd-Y-Zn-Zr alloy with layered heterostructure was used for feasibility verification.Through this method,the optimal microstructures(fine grain,controllable amount of long period stacking ordered(LPSO)structure and nano-scaleβ'precipitates)and the corresponding customized heat treatment processes(520°C/30 min+200°C/48 h)were obtained to achieve a good combination of a high strength of 364 MPa and a considerable elongation of 6.2%,which surpassed those of other state-of-the-art WAAM-processed Mg alloys.Furthermore,we evidenced that the favorable effect of the undeformed LPSO structures on the mechanical properties was emphasized only when the nano-scaleβ'precipitates were present.It is believed that the findings promote the application of magnesium alloy workpieces and help to establish customized heat treatment processes for additively manufactured materials.

Modeling asymmetric fracture mechanics of Mg alloy wire in drawing process

In this study,a numerical analysis was conducted on the ductile fracture of a 2-mm diameter Mg-1Zn-0.5Mn-0.5Sr-0.1Ca alloy wire during drawing.The hexagonally close-packed crystal structure of Mg alloys causes asymmetric fracture behavior,especially in the compression region.The aim of this study is to develop a comprehensive damage model for Mg alloy wire that accurately predicts ductile fracture,with a focus on the compression region.A novel experimental method was introduced to measure the ductile fracture of Mg alloy wires under different stress states.The wire drawing process was simulated using the Generalized Incremental Stress-State dependent damage(GISSMO)Model and the Semi-Analytical Model for Polymers(SAMP)model.The damage model's prediction and the experimental results were found to be in excellent agreement,especially in determining crack initiation.Computational analysis established a safe zone diagram for die angle and reduction ratio,and experimental validation confirmed the feasibility of this approach.The proposed damage model can provide a practical and reliable analysis for optimizing the drawing process of Mg alloy wire.

Enhancing fatigue performance of AZ31 magnesium alloy components fabricated by cold metal transfer-based wire arc directed energy deposition through LPB

Cold Metal Transfer-Based Wire Arc Directed Energy Deposition(CMT-WA-DED)presents a promising avenue for the rapid fabrication of components crucial to automotive,shipbuilding,and aerospace industries.However,the susceptibility to fatigue of CMT-WA-DED-produced AZ31 Mg alloy components has impeded their widespread adoption for critical load-bearing applications.In this study,a comprehensive investigation into the fatigue behaviour of WA-DED-fabricated AZ31 Mg alloy has been carried out and compared to commercially available wrought AZ31 alloy.Our findings indicate that the as-deposited parts exhibit a lower fatigue life than wrought Mg alloy,primarily due to poor surface finish,tensile residual stress,porosity,and coarse grain microstructure inherent in the WA-DED process.Low Plasticity Burnishing(LPB)treatment is applied to mitigate these issues,which induce significant plastic deformation on the surface.This treatment resulted in a remarkable improvement of fatigue life by 42%,accompanied by a reduction in surface roughness,grain refinement and enhancement of compressive residual stress levels.Furthermore,during cyclic deformation,WA-DED specimens exhibited higher plasticity and dislocation density compared to both wrought and WA-DED+LPB specimens.A higher fraction of Low Angle Grain Boundaries(LAGBs)in WA-DED specimens contributed to multiple crack initiation sites and convoluted crack paths,ultimately leading to premature failure.In contrast,wrought and WA-DED+LPB specimens displayed a higher percentage of High Angle Grain Boundaries(HAGBs),which hindered dislocation movement and resulted in fewer crack initiation sites and less complex crack paths,thereby extending fatigue life.These findings underscore the effectiveness of LPB as a post-processing technique to enhance the fatigue performance of WA-DED-fabricated AZ31 Mg alloy components.Our study highlights the importance of LPB surface treatment on AZ31 Mg components produced by CMT-WA-DED to remove surface defects,enabling their widespread use in load-bearing applications.

Effect of grain refinement induced by wire and arc additive manufacture (WAAM) on the corrosion behaviors of AZ31 magnesium alloy in NaCl solution

Additive manufacturing(AM)of Mg alloys has become a promising strategy for producing complex structures,but the corrosion performance of AM Mg components remains unexploited.In this study,wire and arc additive manufacturing(WAAM)was employed to produce single AZ31 layer.The results revealed that the WAAM AZ31 was characterized by significant grain refinement with non-textured crystallographic orientation,similar phase composition and stabilized corrosion performance comparing to the cast AZ31.These varied corrosion behaviors were principally ascribed to the size of grain,where cast AZ31 and WAAM AZ31 were featured by micro galvanic corrosion and intergranular corrosion,respectively.

Enhanced strength-ductility synergy in a wire and arc additively manufactured Mg alloy via tuning interlayer dwell time

Strength-ductility trade-off is a common issue in Mg alloys. This work proposed that a synergistic enhancement of strength and ductility could be achieved through tuning interlayer dwell time(IDT) in the wire and arc additive manufacturing(WAAM) process of Mg alloy.The thermal couples were used to monitor the thermal history during the WAAM process. Additionally, the effect of different IDTs on the microstructure characteristics and resultant mechanical properties of WAAM-processed Mg alloy thin-wall were investigated. The results showed that the stable temperature of the thin-wall component could reach 290 ℃ at IDT=0s, indicating that the thermal accumulation effect was remarkable. Consequently, unimodal coarse grains with an average size of 39.6 μm were generated, and the resultant room-temperature tensile property was poor. With the IDT extended to 60s, the thermal input and thermal dissipation reached a balance, and the stable temperature was only 170 ℃, closing to the initial temperature of the substrate. A refined grain structure with bimodal size distribution was obtained. The remelting zone had fine grains with the size of 15.2 μm, while the arc zone owned coarse grains with the size of 24.5 μm.The alternatively distributed coarse and fine grains lead to the elimination of strength-ductility trade-off. The ultimate tensile strength and elongation of the samples at IDT=60s are increased by 20.6 and 75.0% of those samples at IDT=0s, respectively. The findings will facilitate the development of additive manufacturing processes for advanced Mg alloys.

Study on anisotropy of microstructure and mechanical properties of AZ31 magnesium alloy fabricated by wire arc additive manufacturing

Based on wire arc additive manufacturing(WAAM)technology,AZ31 magnesium alloy in bulk was successfully fabricated,and its microstructure as well as mechanical properties in different planes were observed and analyzed.The AZ31 magnesium alloy has a similar microstructure in the building direction(Z)and travel direction(X),both of which are equiaxed grains.There are heat-affected zones(HAZs)with coarse grains below the fusion line.The second phase is primarily composed of the Mg17Al12 phase,which is evenly distributed in different directions.In addition,the residual stress varies in different directions.There is no significant difference in the hardness of the AZ31 alloy along the Z and X directions,with the average hardness being 68.4 HV and 67.9 HV,respectively.Even though the specimens’ultimate tensile strength along the travel direction is higher in comparison to that along the building direction,their differences in elongation and yield strength are smaller,indicating that the anisotropy of the mechanical properties of the material is small.

Degradable magnesium alloy suture promotes fibrocartilaginous interface regeneration in a rat rotator cuff transosseous repair model

Despite transosseous rotator cuff tear repair using sutures is widely accepted for tendon-bone fixation,the fibrocartilaginous enthesis regeneration is still hardly achieved with the traditional sutures.In the present work,degradable magnesium(Mg)alloy wire was applied to suture supraspinatus tendon in a rat acute rotator cuff tear model with Vicryl Plus 4±0 absorbable suture as control.The shoulder joint humerus-supraspinatus tendon complex specimens were retrieved at 4,8,and 12 weeks after operation.The Mg alloy suture groups showed better biomechanical properties in terms of ultimate load to failure.Gross observation showed that hyperplastic response of the scar tissue at the tendon-bone interface is progressively alleviated over time in the both Mg alloy suture and Vicryl suture groups.In the histological analysis,for Mg alloy suture groups,chondrocytes appear to proliferate at 4 weeks postoperatively,and the tendon-bone interface showed an orderly structural transition zone at 8 weeks postoperatively.The collagenous fiber tended to be aligned and the tendon-bone interlocking structures apparently formed,where transitional structure from unmineralized fibrocartilage to mineralized fibrocartilage was closer to the native fibrocartilaginous enthesis.In vivo degradation of the magnesium alloy wire was completed within 12 weeks.The results indicated that Mg alloy wire was promising as degradable suture with the potential to promotes fibrocartilaginous interface regeneration in rotator cuff repair.

Surface modification of biomedical magnesium alloy wires by micro-arc oxidation

Magnesium alloy wires were processed by micro-arc oxidation （MAO） in a modified silicate-phosphate composite electrolyte containing hydroxyapatite （HA） nanopowders and NaOH. Effects of NaOH content in the composite electrolyte on the microstructure and properties of the MAO ceramic coatings on magnesium alloy wires were studied. It is found that the arc voltage of magnesium alloy wires in the micro-arc oxidation process is significantly reduced while the oxidation rate is accelerated. Addition of 2 g/L NaOH in the composite electrolyte is a better choice for improving corrosion resistance of magnesium alloy wires. During early simulated body fluids （SBF） immersion, the micro-arc oxidized magnesium alloy wires undergo a slow and stable degradation. After soaking for 28 d, the protective ceramic coating still shows no damage but significant degradation is observed for magnesium alloy wires after immersion for more than 60 d.

Microstructure and Mechanical Properties of Wire + Arc Additively Manufactured 2050 Al–Li Alloy Wall Deposits

Aluminum–Lithium(Al–Li) alloy is a topic of great interest owing to its high strength and light weight, but there are only a few applications of Al–Li alloy in wire ss, a special AA2050 Al–Li alloy + arc additive manufacturing(WAAM) process. To identify its feasibility in WAAM procewire was produced and employed in the production of straight-walled components, using a WAAM system based on variable polarity gas tungsten arc welding(VP-GTAW) process. The influence of post-deposited heat treatment on the microstructure and property of the deposit was investigated using optical micrographs(OM), scanning electron microscopy(SEM), X-ray diffraction(XRD), hardness and tensile properties tests. Results revealed that the microstructures of AA2050 aluminum deposits varied with their location layers. The upper layers consisted of fine equiaxed grains, while the bottom layer exhibited a coarse columnar structure. Mechanical properties witnessed a significant improvement after post-deposited heat treatment, with the average micro-hardness reaching 141 HV and the ultimate tensile strength exceeding 400 MPa. Fracture morphology exhibited a typical ductile fracture.

Characteristic of laser-MIG hybrid welding with filling additional cold wire for aluminum alloy

The weld appearance, deposition rate, welding efficiency, stability of arc, laser keyhole characteristic, and weld property were studied by using a novel laser-MIG hybrid welding process with filling wire of aluminum alloy. The results were also compared with those by conventional laser-MIG hybrid welding process. It was found that with the suitable process parameters this novel welding process for aluminum alloy was stable and final weld bead had fine appearance. Compared to conventional laser-MIG hybrid welding process, during this novel welding process the stability of arc, the laser keyhole characteristic and the weld property were similar, while the keyhole cycle frequency and keyhole opening area had differences of 1.23% and 15.34%, respectively, and the welding efficiency increased by about 31% without increasing heat input.

Effect of filler wire on the joint properties of AZ31 magnesium alloys using CO_2 laser welding

Laser welding with filler wire of AZ31 magnesium alloys is investigated using a CO2 laser experimental system. The effect of three different filler wires on the joint properties is researched. The results show that the weld appearance can be effectively improved when using laser welding with filler wire. The microhardness and tensile strength of joints are almost the same us those of the base metal when ER AZ31 or ER AZ61 wire is adopted. However, when the filler wire of ER 5356 aluminum alloy is used, the mechanical properties of flints become worse. For ER AZ31 and ER AZ61 filler wires, the microstructure of weld zone slws small dendrite grains. In comparison, for ER 5356 filler wire, the weld shows a structure of snowy dendrites and many intermetallic compounds and eutectic phases distribute in the dendrites. These intermetallic constituents with low melting point increase the tendency of hot crack and result in fiagile joint properties. Therefore, ER AZ31 and ER AZ61 wire are more suitable filler material than ER 5356 for CO2 laser welding of AZ31 magnesium alloys.

A comparative study of the role of solute,potent particles and ultrasonic treatment during solidification of pure Mg,Mg-Zn and Mg-Zr alloys

Ultrasonic treatment(UST)applied during the solidification of pure Mg,eutectic(Mg-Zn)and peritectic(Mg-Zr)alloys was investigated in order to explore the grain refinement mechanisms.Temperature dependent grain refinement is observed in pure Mg where decreasing the superheat temperature(at which UST is applied from above the melting temperature,TM)from 100℃to 40℃produces significant refinement with a uniform grain structure.The presence of solute reduces the temperature dependence of the UST refinement and excellent grain refinement is obtained regardless of the superheat temperature(100℃or 40℃)and even with the use of preheated sonotrode in the Mg-6 wt.%Zn alloy.A further improvement in grain refinement is achieved when the alloy contains potent particles that introduce additional nucleation of grains in Mg-0.5 and 1.0 wt.%Zr alloys(producing an average grain size of≤100μm).At 40℃superheat,UST of Mg-Zn alloys produces excellent refinement(average grain size<200μm)with non-dendritic grains,which is normally achieved only with the addition of grain refining master alloy in the as-cast condition.The enhanced refinement observed in the eutectic alloy is explained through the undercooling imposed by a relatively cold sonotrode combined with high frequency vibrations and acoustic streaming.The advantages of using a cold sonotrode,a low superheat and solute are demonstrated for achieving significant refinement during solidification of Mg alloys under UST without or with a lower addition of grain refining master alloys.

Formability,microstructure evolution and mechanical properties of wire arc additively manufactured AZ80M magnesium alloy using gas tungsten arc welding

Wire arc additive manufacturing(WAAM)technology has been used to fabricate the multi-layer single-pass deposited wall of AZ80M magnesium(Mg)alloy by gas tungsten arc welding.The formability,thermal cycles,microstructural evolution and mechanical properties of the WAAM AZ80M Mg alloy were investigated.The results show that there was significant difference in the temperature variation and the geometries between the original several layers and the subsequent deposited layers.Owing to the arc energy input,the interpass temperature rised rapidly and then stabilized at 150℃.As a result,the width of the deposited wall increased and then kept stable.There were obvious differences in the microstructure of the WAAM AZ80M Mg alloy among the top zone,intermediate zone and bottom zone of deposited wall.During the arc deposition process,theβphase of the WAAM AZ80M Mg alloy redissolved due to the cyclic heat accumulation,and then precipitated in the grain boundary.The cyclic heat accumulation also led to weakening of dendrite segregation.From the substrate to the top zone,the hardness of the deposited wall decreased gradually,and the intermediate zone which was the main body of deposited wall had relatively uniform hardness.The tensile properties of the WAAM AZ80M Mg alloy were different between the vertical direction and the horizontal direction.And the maximum ultimate tensile strength of the WAAM AZ80M Mg alloy was 308 MPa which was close to that of the as-extruded AZ80M Mg alloy.

Influence of alloying elements on hot tearing susceptibility of Mg-Zn alloys based on thermodynamic calculation and experimental

Based on the hot tearing index|△T/△(fs)^(0.5)|recently proposed by Kou and the thermodynamic calculations of Pandat software,Al,Cu,and Mn elements were picked up and their influence on hot tearing susceptibility of Mg-x Zn(x=6,8,10,wt%)alloys was studied by experiments.The results indicate that Al addition can significantly reduce the hot tearing susceptibility of Mg-Zn alloys.Either 0.5Cu or 0.3Mn addition individually can reduce the HTS of the Mg-6Zn-(1,4)Al alloys,while adding together increases the susceptibility.The addition of 0.5Cu and 0.3Mn both individually and together increases the HTS of Mg-8/10Zn-1Al alloys.Based on the experimental and calculation results,the index can be modified to|△T/△(fs)^(0.5)|(d)^(2)for more accurate prediction on the hot tearing resistance of Mg-Zn based alloys.Grain refinement significantly improves the hot tearing resistance of Mg-Zn based alloys.

A comparison study of Ce/La and Ca microalloying on the bio-corrosion behaviors of extruded Mg-Zn alloys

The influences of Ca and Ce/La microalloying on the microstructure evolution and bio-corrosion resistances of extruded Mg-Zn alloys have been systematically investigated in the current study.Compared with single Ca or Ce/La addition,the Ca-Ce/La cooperative microalloying results in an outstanding grain refinement,because the fine secondary phase particles effectively hinder the recrystallized grain growth.The coarse Ca2Mg6Zn3 phases promote the formation of Ca3(PO4)2 or hydroxyapatite particles during the immersion process and accelerate the dissolution of the corrosion product film,which destroys its integrity and results in the deterioration of anti-corrosive performance.The Ce/La elements can be dispersed within the conventional Mg7Zn3 phases,which reduce the internal galvanic corrosion between Mg matrix and the secondary phases,leading to an obvious improvement of corrosion resistance.Therefore,the Ca-Ce/La cooperative microalloying achieves a homogenous fine-grained microstructure and improves the protective ability of surface film,which will pave a new avenue for the design of biomedical Mg alloys in the coming future.

Effects of Cd addition in welding wires on microstructure and mechanical property of wire and arc additively manufactured Al-Cu alloy

Wall structures were made by cold metal transfer-based wire and arc additive manufacturing using two kinds of ER2319 welding wires with and without Cd elements. T6 heat treatment was used to improve mechanical properties of these wall structures. Due to the higher vacancy binding energy of Cd, Cd-vacancy clusters are formed in the aging process and provide a large number of nucleation locations for θ′ phases. The higher diffusion coefficient of the Cd-vacancy cluster and the lower interfacial energy of θ′ phase lead to the formation of dense θ′ phases in the heat-treated α(Al). According to the strengthening model, after adding Cd in ER2319 welding wires, the yield strength increases by 43 MPa in the building direction of the heat-treated wall structures.

Effect of heat treatment on the microstructure and mechanical properties of AZ80M magnesium alloy fabricated by wire arc additive manufacturing

To maximize the benefits of wire arc additive manufacturing(WAAM)processes,the effect of post-deposition heat treatment on the microstructure and mechanical properties of WAAM AZ80M magnesium(Mg)alloy was investigated.Three different heat treatment procedures(T4,T5 and T6)were performed.According to the results,after T4 heat treatment,the microsegregation of alloying elements was improved with the eutectic structure dissolved.Samples after T5 heat treatment inherited the net-like distribution of secondary phases similar to the as-deposited sample,where the eutectic structure covering the interdendritic regions and theβ-phase precipitated around the eutectic structure.After T6 heat treatment,the tinyβ-phases re-precipitated from the matrix and distributed in inner and outer of the grains.The hardness distribution of the samples went through T4 and T6 heat treatment was more uniform in comparison to that of T5 heat treated samples.The tensile test showed that the T6 heat treatment improved the strength and ductility,and the anisotropy between horizontal and vertical can be eliminated.Moreover,T4 treated samples exhibited highest ductility.

Investigation of dry sliding wear properties of multi-directional forged Mg-Zn alloys

Effect of multi-directional forging(MDF)on wear properties of Mg-Zn alloys(with 2,4,and 6wt%Zn)is investigated.Dry sliding wear test was performed using pin on disk machine on MDF processed and homogenized samples.Wear behavior of samples was analyzed at loads of ION and 20 N,with sliding distances of 2000m and 4000m,at a sliding velocity of 3m/s.Microstructures of worn samples were observed under scanning electron microscopy(SEM),energy dispersive spectroscopy(EDS),and x-ray diffraction(XRD)and the results were analyzed.Mechanical properties were evaluated using microhardness test.After 5 passes of MDF,the average grain size was found to be 30±4p m,22±3 pm,and 18±3 pm,in Mg-2%Zn,Mg-4%Zn,and Mg-6%Zn alloys,respectively,with significant improvement in hardness in all cases.Wear resistance was improved after MDF processing,as well as,with increment in Zn content in Mg alloy.However,it decreased when the load and the sliding distance increased.Worn surface exhibited ploughing,delamination,plastic deformation,and wear debris along sliding direction,and abrasive wear was found to be the main mechanism.