Exploring a balance between strength and ductility of hexagonal BN nanoplatelet reinforced ZK61 magnesium composite

The practical applications of magnesium(Mg)alloys are usually beset by their relatively low strength and limited ductility.Herein we attempt to fabricate hexagonal BN nanoplatelet(BNNP)reinforced ZK61 magnesium composites using a combination of spark plasma sintering and friction stir processing.The resulting composites exhibit microstructural characteristics of homogeneous dispersion of BNNP in Mg matrix with refined equiaxed grains and(0002)basal texture roughly surrounding the pin column surface.Transmission electron microscopy observation illustrates that trace amounts of Mg_(3)N_(2)and MgB_(2)form at BNNP-Mg interface,in which Mg_(3)N_(2)locates at the basal plane of a BNNP and MgB_(2)grows at its open edge.The spatial distribution of Mg_(3)N_(2)and MgB_(2)facilitates interfacial wetting and stronger BNNP-Mg interface in such a way that interfacial products act as anchors bonding between them.In comparison with monolithic ZK61 alloy,the BNNP/ZK61 composites display simultaneous improvements in yield strength,hardness and ductility,achieving good strength-ductility balance.This research is expected to shed some light on BNNP potentials for designing and producing magnesium composites with high strength and good ductility.

The deteriorated degradation resistance of Mg alloy microtubes for vascular stent under the coupling effect of radial compressive stress and dynamic medium

The degradation of Mg alloys relates to the service performance of Mg alloy biodegradable implants.In order to investigate the degradation behavior of Mg alloys as vascular stent materials in the near service environment,the hot-extruded fine-grained Mg-Zn-Y-Nd alloy microtubes,which are employed to manufacture vascular stents,were tested under radial compressive stress in the dynamic Hanks'Balanced Salt Solution(HBSS).The results revealed that the high flow rate accelerates the degradation of Mg alloy microtubes and its degradation is sensitive to radial compressive stress.These results contribute to understanding the service performance of Mg alloys as vascular stent materials.

A multi-functional MgF_(2)/polydopamine/hyaluronan-astaxanthin coating on the biodegradable ZE21B alloy with better corrosion resistance and biocompatibility for cardiovascular application

The cardiovascular diseases(CVD)continue to be the major threat to global public health over the years,while one of the effective methods to treat CVD is stent intervention.Biomedical magnesium(Mg)alloys have great potential applications in cardiovascular stents benefit from their excellent biodegradability and absorbability.However,excessive degradation rate and the delayed surface endothelialization still limit their further application.In this study,we modified a Mg-Zn-Y-Nd alloy(ZE21B)by preparing MgF_(2) as the corrosion resistance layer,the dopamine polymer film(PDA)as the bonding layer,and hyaluronic acid(HA)loaded astaxanthin(ASTA)as an important layer to directing the cardiovascular cells fate.The electrochemical test results showed that the MgF_(2)/PDA/HA-ASTA coating improved the corrosion resistance of ZE21B.The cytocompatibility experiments also demonstrated that this novel composite coating also selectively promoted endothelial cells proliferation,inhibited hyperproliferation of smooth muscle cells and adhesion of macrophages.Compared with the HAloaded rapamycin(RAPA)coating,our MgF_(2)/PDA/HA-ASTA coating showed better blood compatibility and cytocompatibility,indicating stronger multi-functions for the ZE21B alloy on cardiovascular application.

The misalignment between degradation rate and mechanical integrity of Mg-Zn-Y-Nd alloy during the degradation evaluation in modified Hanks’solutions

The degradation behavior of biodegradable Mg alloys has become a research hotspot in the fields about biodegradable metallic materials.While the most of the related publications mainly focused on the degradation rate of Mg-based materials,but rare to care about the changes of their mechanical properties during the immersion period,which can significantly affect their service performance.The link between residual strength and Mg degradation is not appreciated enough.In this work,a series media were constructed based on Hanks’solution,the effects of inorganic ions on the degradation rate and mechanical integrity of Mg-Zn-Y-Nd alloy were investigated.The results indicated that the degradation behavior of Mg alloy was mainly controlled by degradation products and there is no direct correspondence between the degradation rate change and mechanical integrity of Mg alloy.The relevant findings are beneficial for selecting the monitoring index in Mg corrosion tests and evaluating the service reliability of Mg alloys for biomedical applications.

Mg alloy cardio-/cerebrovascular scaffolds: Developments and prospects

Vascular scaffolds are one of the important application fields of biodegradable Mg alloys, and related research has been carried out for more than 20 years. In recent years, the application expansion of Mg alloy vascular scaffolds has brought new challenges to the research of related fields. This review focuses on the relevant advances in the field of Mg alloys for both cardio-/cerebrovascular scaffolds. The frequently investigated alloy series for vascular scaffolds were reviewed. The bottleneck of processing of Mg alloy minitubes was elucidated.The idea of functionalized surface modification was also pointed out in this review, and the authors put forward guidelines based on research experience in terms of scaffold structural design and degradation behavior evaluation. Finally, suggestions for further research directions of Mg alloy vascular scaffolds were provided.

Initial micro-galvanic corrosion behavior between Mg_(2)Ca and α-Mg via quasi-in situ SEM approach and first-principles calculation

The initial micro-galvanic corrosion behavior of Mg-30wt%Ca alloy only containing Mg_(2)Ca andα-Mg was studied by immersion testing in a 0.9%Na Cl solution at 37°C.The quasi-in situ SEM and TEM results show that Mg_(2)Ca corroded easier thanα-Mg,indicating that Mg_(2)Ca acted as an anode.The work function(Φ)for Mg_(2)Ca calculated by first-principles is significantly lower compared to that forα-Mg.The Volta potential measured by a scanning Kelvin probe force microscope reveals that the Mg_(2)Ca had a relatively low Volta potential(ψ)value.The lowerΦandψvalues for Mg_(2)Ca indicate a lower electrochemical nobility,which is consistent with the experimental phenomenon.

A promoting nitric oxide-releasing coating containing copper ion on ZE21B alloy for potential vascular stent application

Magnesium-based biodegradable metals as cardiovascular stents have shown a lot of excellent performance, which have been used to treat coronary artery diseases. However, the excessive degradation rate, imperfect biocompatibility and delayed re-endothelialization still lead to a considerable challenge for its application. In this work, to overcome these shortcomings, a compound of catalyzing nitric oxide(NO) generation containing copper ions(Cu^(2+)) and hyaluronic acid(HA), an important component of the extracellular matrix, were covalently immobilized on a hydrofluoric acid(HF)-pretreated ZE21B alloy via amination layer for improving its corrosion resistance and endothelialization. Specifically,the Cu^(2+) chelated firmly with a cyclen 1,4,7,10-tetraazacyclododecane-N’, N’’, N’’’, N-tetraacetic acid(DOTA) could form a stability of hybrid coating, avoiding the explosion of Cu^(2+). The chelated Cu^(2+) enabled the catalytic generation of NO and promoted the adhesion and proliferation of endothelial cells(ECs) in vascular micro-environment. In this case, the synergistic effect of NO-generation and endothelial glycocalyx molecules of HA lead to efficient ECs promotion and smooth muscle cells(SMCs) inhibition. Meanwhile, the blood compatibility also had achieved a marked improvement. Moreover, the standard electrochemical measurements indicated that the functionalized ZE21B alloy had better anti-corrosion ability. In a conclusion, the dual-functional coating displays a great potential in the field of biodegradable magnesium-based implantable cardiovascular stents.

Effect of rare earth and Mn elements on the corrosion behavior of extruded AZ61 system in 3.5 wt%NaCl solution and salt spray test

In this study,multiple addition of rare earth(RE)and manganese(Mn)to AZ61 was conducted aiming to find out the influence to corrosion resistance.AZ61 containing different amounts of RE and Mn was investigated by electrochemical measurement in condition of 3.5 wt%NaCl solution at 25°C.Gravimetric measurement was conducted in 5 wt%salt spray at 35°C and 3.5 wt%NaCl solution at 25°C.Samples were characterized by SEM,EDS,OM and XRD.The result shows that with RE addition Al8Mn5 in AZ61 changed into Al10RE2Mn7.The quantity ofβphase is reduced significantly.The multiple addition of RE and Mn improved the corrosion resistance of AZ61.When the ratio of Mn and RE is 0.3,alloy has the best property of corrosion resistance.In addition,the composite addition removed the impurity elements in AZ61 especially Fe.

Corrosion fatigue of the extruded Mg-Zn-Y-Nd alloy in simulated body fluid

Magnesium alloys were considered to be used as biodegradable implants due to their biocompatibility,biodegradability and nontoxicity.However,under the simultaneous action of corrosive environment and mechanical loading in human body,magnesium alloys are easy to be affected by corrosion fatigue and stress corrosion cracking.In this work,the fatigue behavior of the extruded Mg-Zn-Y-Nd alloy used for vascular stents was studied both in air and in simulated body fluid(SBF).It was revealed that the fatigue limit of as-extruded Mg-Zn-Y-Nd alloy in air is about 65 MPa at 10^7 cycles,while there is no limit in SBF and shows a linear relationship between the fatigue life and stress amplitudes.The fatigue crack source in air was formed by the inclusions and defects.However,the stress corrosion and hydrogen embrittlement are the main reasons for the formation of the fatigue initial crack source in SBF.

Microstructure and texture evolution of fine-grained Mg-Zn-Y-Nd alloy micro-tubes for biodegradable vascular stents processed by hot extrusion and rapid cooling

Magnesium alloys have narrow available slip result from close-packed hexagonal structure that limit their processing properties.In the recent work,the Mg-2Zn-0.46Y-0.5Nd,as materials for degradable stents,was applied to produce as-extruded micro-tube with an outer diameter of 3.0mm and a wall thickness of 0.35mm by hot extrusion with an extrusion ratio of 105:1 at 653K and rapid cooling.The fine microstructure of the dynamic recrystallization of as-extruded micro-tube could be preserved by rapid cooling such as water-cooled,resulting in more excellent mechanical properties relative to air-cooled micro-tube.The addition of rare earth elements Y and Nd results in continuous dynamic recrystallization dominated the dynamic recrystallization mechanism.During the hot extrusion process,the activation of the non-basal slip system,especially the pyramidal(c+a)slip,could significantly weaken the texture strength,and the as-extruded micro-tube exhibits weak"RE"texture components(011^(-)1)||ED and(1^(-)21^(-)1)||ED.Hence,the magnesium alloy micro-tube prepared by the rapid cooling has fine microstructure and weak texture,which is favorable for further process and governance.

A two-step superplastic forging forming of semi-continuously cast AZ70 magnesium alloy

A two-step technology combined forging with superplastic forming has been developed to enhance the forgeability of semi-continuously cast AZ70 magnesium alloy and realize the application of the as-cast magnesium alloy in large deformation bullet shell.In the first step,fine-grained microstructure preforms that are suitable for superplastic forming were obtained by reasonably designing the size of the initial blanks with the specific height-to-diameter ratio,upsetting the blanks and subsequent annealing.In the second step,the heat treated preforms were forged into the end products at the superplastic conditions.The end products exhibit high quality surface and satisfied microstructure.Consequently,this forming technology that not only avoids complicating the material preparation but also utilizes higher strain rate superplastic provides a near net-shaped novel method on magnesium forging forming technology using as-cast billet.

In vitro corrosion properties of HTHEed Mg-Zn-Y-Nd alloy microtubes for stent applications:Influence of second phase particles and crystal orientation

Magnesium(Mg)alloys are promising materials for cardiovascular stent applications due to their good biocompatibility and biodegradability.However,in vitro and in vivo corrosion tests reveal that Mg alloy stents suffer from a rapid corrosion rate and severe localized corrosion,which is limiting their widespread application.To solve the problem of uneven degradation of stents,a HTHE(long-time and high-temperature heat treatment,large-reduction-ratio hot extrusion)process is used to manufacture Mg-Zn-Y-Nd alloy microtubes in this study.The heat treatment is to dissolve alloying elements and reduce the size of SPPs,and the hot extrusion is to acquire fine-grained and strongly textured microtubes.The microstructural characterization shows that coarse second phases in as-cast alloy are refined and uniformly distributed in matrix of microtubes.After hot extrusion,microtubes show strong texture with basal plain oriented parallel to the longitudinal section(LS).The corrosion testing indicates that severe localized corrosion occurs on the cross section(CS)while localized corrosion is alleviated on the LS.Based on the different corrosion properties of the LS and CS,HTHEed microtubes are promising for solving the problems of rapid corrosion rate and severe localized corrosion of Mg alloy stents.

Preparation of functional coating on magnesium alloy with hydrophilic polymers and bioactive peptides for improved corrosion resistance and biocompatibility

Biodegradable magnesium alloy stents(MAS)have great potential in the treatment of cardiovascular diseases.However,too fast degradation and the poor biocompatibility are still two key problems for the clinical utility of MAS.In the present work,a functional coating composed of hydrophilic polymers and bioactive peptides was constructed on magnesium alloy to improve its corrosion resistance and biocompatibility in vitro and in vivo.Mg-Zn-Y-Nd(ZE21B)alloy modified with the functional coating exhibited moderate surface hydrophilicity and enhanced corrosion resistance.The favourable hemocompatibility of ZE21B alloy with the functional coating was confirmed by the in vitro blood experiments.Moreover,the modified ZE21B alloy could selectively promote the adhesion,proliferation,and migration of endothelial cells(ECs),but suppress these behaviors of smooth muscle cells(SMCs).Furthermore,the modified ZE21B alloy wires could alleviate intimal hyperplasia,enhance corrosion resistance and re-endothelialization in vivo transplantation experiment.These results collectively demonstrated that the functional coating improved the corrosion resistance and biocompatibility of ZE21B alloy.This functional coating provides new insight into the design and development of novel biodegradable stents for biomedical engineering.

Degradation of Mg-Zn-Y-Nd alloy intestinal stent and its effect on the growth of intestinal endothelial tissue in rabbit model

Biodegradable magnesium alloys have excellent properties with respect to biodegradability, biocompatibility, and biomechanics, which may indicate a possibility of its application in intestinal stents. Investigation of Mg-Zn-Y-Nd alloy’s application in intestinal stents has been performed. This study aims to investigate the degradation behavior of Mg-Zn-Y-Nd alloy intestinal stents coated with poly(L-lactide)/paclitaxel in the intestinal environment and its biocompatibility with intestinal tissue. In this paper, Mg-Zn-Y-Nd alloy’s corrosion properties were evaluated by the immersion test in human feces, SEM and XRD, and animal tests. In vitro results showed that when the Mg-Zn-Y-Nd alloy was immersed in human feces for two weeks, its corrosion resistance could be improved by micro arc oxidation(MAO) and poly-l-lactide(PLLA) dual coating. Additionally, this result was also confirmed in vivo experiments by rabbit model. And animal tests also demonstrated that the Mg-Zn-Y-Nd alloy with MAO/PLLA/paclitaxel dual coating drug-eluting stents could inhibit the proliferation of local intestinal tissue around the stents. However, in vivo studies illustrated that the intestinal stents gradually degraded in rabbit model within 12 days.Considering the degradation rate of the stent was faster than expected in rabbits, the support performance of the scaffold requires further improvement.

In vitro and in vivo studies on pure Mg, Mg-1Ca and Mg-2Sr alloys processed by equal channel angular pressing

In the present work,the biomedical as-cast pure Mg,Mg–1 Ca and Mg–2 Sr alloys were processed with equal channel angular pressing(ECAP)technique to develop ultrafine microstructure within the materials,and their microstructures,mechanical properties,degradation behavior,cytocompatibility in vitro and biocompatibility in vivo were studied comprehensively.Finer-gained microstructures and improved mechanical properties of these three materials after ECAP were confirmed compared to their as-cast counterparts.Moreover,after ECAP the degradation rate of pure Mg was increased while that of Mg–1 Ca or Mg–2 Sr alloys decreased compared to the ascast counterparts.Additionally,good in vitro cytocompatibility and in vivo biocompatibility of these three materials were revealed by cell cultural tests using osteoblastic MC3 T3-E1 and human mesenchymal stem cells(h MSC)and in vivo animal tests at the lateral epicondyle of SD-rats’femur.This study offers an alternative powerful avenue to achieve good comprehensive properties of magnesium-based biodegradable metals.It might also help to extend the applied range of magnesium-based biodegradable metals in orthopedic field.

Zn content mediated fibrinogen adsorption on biodegradable Mg-Zn alloys surfaces

The protein adsorption has an immense influence on the biocompatibility of biodegradable Mg alloy.In this work,the effect of Zn content on the fibrinogen(Fg)adsorption behavior in Mg-Zn binary alloy was systematically investigated.Experimental results showed that the Fg adsorption amount increased at first and then decreased with the increase of Zn content.The adsorption mechanism was investigated by molecular dynamic and density functional theory simulations.The simulations results showed that Zn with low content existed in the inner layer of Mg alloys due to the lower system energy,which promoted Fg adsorption and the promotion effect was more obvious with the increase of Zn content.When Zn content increased to a higher concentration,parts of Zn atoms started to precipitate in the surface,and the Fg-surface interaction energy started to increase.Moreover,the Zn sites favored the formation of ordered water molecules layers,which inhibit the stable adsorptions of Fg.The inhibition effects of Fg adsorption was enhanced with the Zn content increase.In short,the simulation results explain the experimental phenomena and reveal the microscopic mechanism.This study would provide a significant guidance on the design of biodegradable Mg-Zn alloys.

Rapid-developing Mg-based biodegradable materials:The editorial of the special issue on Mg-based functional materials-biomaterials section

Since physician Edward C.Huse firstly tried to stop bleeding blood vessels with Mg wires in 1878[1],the history of Mg and its alloys as biomaterials has gone through more than 140 years.Especially,in the latest 20 years,scientists from all over the world have carried out all-around research on Mg-based materials for the applications of vascular stents.

Effect of Rolling Temperature on the Mechanical Properties and Corrosion Behavior of Mg-Zn-Y-Nd Alloy Thin Sheets

There is a growing demand for degradable membranes with sufficient mechanical properties to guide tissue regeneration in dental surgery.In the present work,a two-stage rolling process in which the first rolling stage(FRS)adopted a reduction rate of 30%for six passes at various temperatures,while the second rolling stage was rolling at 200℃for two passes,was employed to prepare a 150μm-grade Mg-2.0Zn-0.5Y-0.5Nd(ZE21B)Mg alloy sheets for guided tissue regeneration membrane.The microstructure of the thin sheets was gradually refined with increasing rolling passes,and the thin sheets that were rolled at different FRS temperatures exhibit an ellipse texture.The thin sheets rolled at 350℃for FRS show low elongation due to premature fracture caused by the coarse second phase particles.On account of uniform and fine grains,the thin sheets rolled at 400℃for the FRS have proper mechanical properties:yield strength of 214.6±8.5 MPa,ultimate tensile strength(UTS)of 246.8±10.3 MPa and elongation to failure of 28.3±1.2%.When rolling at 450℃for FRS,proper ductility of the thin sheets has been acquired,followed by a decline in UTS since a bimodal structure with fine and coarse grain was developed.Immersion tests demonstrated the FRS temperature had no significant effect on the corrosion behavior and corrosion rate of Mg alloy sheets after 7 days’immersion in artificial saliva solution.This research has great significance for the production of degradable Mg sheets for guided tissue regeneration membrane.

Effect of Ca Micro-Alloying on the Microstructure and Anti-Corrosion Property of Mg0.5Zn0.2Ge Alloy

Magnesium and its alloys have attracting rising attention as one of biodegradable metallic materials.However,the rapid corrosion and severe localized corrosion still hinder their extensive applications in clinics.In this study,micro-alloying of Ca(≤0.1 wt%)into Mg0.5Zn0.2Ge alloy developed in our previous work was explored to further enhance the corrosion resistance and alleviate the localized corrosion of the alloy.The results reveal that the addition of Ca leads to the transformation of the cathodic Mg_(2)Ge phase in Mg0.5Zn0.2Ca alloy into anodic MgCaGe phase in Ca-containing alloys,thereby changing the galvanic couples in alloys during immersion.The preferential dissolution of MgCaGe phase promotes the participation of Ca and Ge into the formation of corrosion products,resulting in the enrichment of Ca and Ge in the outmost of corrosion product layer,which stabilizes and passivates the corrosion product layer on Mg alloy surface.Additionally,the enrichment of Zn at the corrosion interface seems to further hinder the corrosion of Mg matrix.All of these factors confer a slower and more uniform corrosion on Mg0.5Zn0.2GexCa(x<0.1 wt%)alloy,which provides favorable candidates for the further processing to gain suitable biodegradable Mg alloys.

Degradation behavior of ZE21C magnesium alloy suture anchors and their effect on ligament-bone junction repair

Current materials comprising suture anchors used to reconstruct ligament-bone junctions still have limitation in biocompatibility,degradability or mechanical properties.Magnesium alloys are potential bone implant materials,and Mg^(2+) has been shown to promote ligament-bone healing.Here,we used Mg-2 wt.%Zn-0.5 wt.%Y-1 wt.%Nd-0.5 wt.%Zr(ZE21C)alloy and Ti6Al4V(TC4)alloy to prepare suture anchors to reconstruct the patellar ligament-tibia in SD rats.We studied the degradation behavior of the ZE21C suture anchor via in vitro and in vivo experiments and assessed its reparative effect on the ligament-bone junction.In vitro,the ZE21C suture anchor degraded gradually,and calcium and phosphorus products accumulated on its surface during degradation.In vivo,the ZE21C suture anchor could maintain its mechanical integrity within 12 weeks of implantation in rats.The tail of the ZE21C suture anchor in high stress concentration degraded rapidly during the early implantation stage(0-4weeks),while bone healing accelerated the degradation of the anchor head in the late implantation stage(4-12weeks).Radiological,histological,and biomechanical assays indicated that the ZE21C suture anchor promoted bone healing above the suture anchor and fibrocartilaginous interface regeneration in the ligament-bone junction,leading to better biomechanical strength than the TC4 group.Hence,this study provides a basis for further research on the clinical application of degradable magnesium alloy suture anchors.