Application of novel constrained friction processing method to produce fine grained biomedical Mg-Zn-Ca alloy

In order to obtain Mg alloys with fine microstructures and high mechanical performances,a novel friction-based processing method,name as“constrained friction processing(CFP)”,was investigated.Via CFP,defect-free Mg-Zn-Ca rods with greatly refined grains and high mechanical properties were produced.Compared to the previous as-cast microstructure,the grain size was reduced from more than 1 mm to around 4μm within 3 s by a single process cycle.The compressive yield strength was increased by 350%while the ultimate compressive strength by 53%.According to the established material flow behaviors by“tracer material”,the plastic material was transported by shear deformation.From the base material to the rod,the material experienced three stages,i.e.deformation by the tool,upward flow with additional tilt,followed by upward transportation.The microstructural evolution was revealed by“stop-action”technique.The microstructural development at regions adjacent to the rod is mainly controlled by twinning,dynamic recrystallization(DRX)as well as particle stimulated nucleation,while that within the rod is related to DRX combined with grain growth.

Effect of the microstructure parameters on the corrosion characteristics of Mg-Zn-Ca alloy with columnar structure

Magnesium alloys with homogeneous degradation and controlled degradation rate are desirable for biodegradable materials.In the present work,Mg-3 wt.%Zn-0.2 wt.%Ca alloys with different columnar structures were fabricated and the degradation in 0.9 wt.%NaCl were investigated.With the increase of the growth rate for the directional solidification,the microstructure of the directionally solidified(DSed)alloy evolved from cellular to dendritic coupled with the change of the spacing of the primary trunks(λ_(1))and the volume fraction(fv)of Ca_(2)Mg_(6)Zn_(3) phase.The results of the corrosion test suggested that the alloy with cellular structure experienced homogeneous corrosion and exhibited the lowest corrosion rate.The good corrosion resistance of the alloy with cellular structure was attributed to the protective corrosion products film(CPF),which was closely related to the fv of Ca_(2)Mg_(6)Zn_(3) phase andλ_(1).To evaluate the corrosion rates(CR)of the DSed Mg-Zn-Ca alloys with different microstructures,a parameterαwas proposed in this work,which was calculated byλ_(1) and the fv of Ca_(2)Mg_(6)Zn_(3) phase.The fitting result showed that there was a linear relationship between CR andα,which was CR=4.1899+0.00432α.This means that the CR of the DSed Mg-Zn-Ca alloy can be evaluated if the microstructure had been characterized.

Effects of cooling rate on microstructure,mechanical and corrosion properties of Mg-Zn-Ca alloy

Mg69Zn27Ca4 alloys with diameters of 1.5, 2 and 3 mm were fabricated using copper mold injection casting method. Microstructural analysis reveals that the alloy with a diameter of 1.5 mm is almost completely composed of amorphous phase. However, with the cooling rate decline, a little α-Mg and MgZn dendrites can be found in the amorphous matrix. Based on the microstructural and tensile results, the ductile dendrites are conceived to be highly responsible for the enhanced compressive strain from 1.3% to 3.1% by increasing the sample diameter from 1.5 mm to 3 mm. In addition, the Mg69Zn27Ca4 alloy with 1.5 mm diameter has the best corrosion properties. The current Mg-based alloys show much better corrosion resistance than the traditionally commercial wrought magnesium alloy ZK60 in simulated sea-water.

Reducing the tension-compression yield asymmetry of extruded Mg-Zn-Ca alloy via equal channel angular pressing

The influence of equal channel angular pressing on the tension-compression yield asymmetry of extruded Mg-5.3 Zn-0.6 Ca(weight percent)alloy has been investigated.The microstructure was obviously refined by the large strain during the equal channel angular pressing,accompanied with very fine Ca_(2)Mg_(6)Zn_(3) phases with average diameter of 70 nm.The weak tension-compression yield asymmetry after equal channel angular pressing is mainly attributed to the reduced volume fraction of extension twinning during the compression,because the slope(k)of twinning in Hall-Petch relationship is higher than that of dislocation slip,and the twinning deformation is difficult to take place with decreasing grain size.The basal slip is more active in the alloy after equal channel angular pressing,due to the non-basal texture components,which hinders the twinning activation and reduces the yield asymmetry.Furthermore,the presence of fine precipitate restricts the twinning activation,which also contributes to the reduction of yield asymmetry.

Exploration of the enhanced performances for silk fibroin/sodium alginate composite coatings on biodegradable Mg-Zn-Ca alloy

To expand the future clinic applications of biodegradable magnesium alloy,polymer coatings with excellent biocompatibility are the keys to solve the local alkalinity and rapid hydrogen release.Natural-organic silk fibroin provides an approach to fabricate a protective coating on biomedical Mg-Zn-Ca alloy,however,the adhesion force and mechanical properties of the coating on substrates are ought to be further improved without any chemical conversion/intermediate layer.Hereby,based on VUV/O;surface activation,a hybrid of silk fibroin and sodium alginate is proposed to enhance the adhesion force and mechanical properties of the composite coatings on hydrophilic Mg-Zn-Ca alloy surfaces.Various mass ratios of sodium alginate addition were investigated to achieve the optimum coating strategy.The nanoscratch test and nanoindentation test confirmed that the adhesion force was tripled and mechanical properties index was significantly improved when the mass ratio of silk fibroin/sodium alginate was 70/30 compared to pure silk fibroin or sodium alginate coatings.Meanwhile,the corrosion rate of the coated Mg-Zn-Ca alloy was significantly delayed with the addition of sodium alginate,resulting in a reaction layer during corrosion process.Furthermore,the mechanisms for both adhesion and corrosion processes were discussed in detail.Our findings offer more possibilities for the controllable surface performance of degradable metals.

Microstructures and properties of rapidly solidified Mg-Zn-Ca alloys

Ternary alloys based on the Mg-Zn-Ca system were produced by twin-roll rapid solidification.The alloys were characterized by OM,SEM,HRTEM,XRD,EDS and Micro-hardness.The results show that the rapidly solidified flakes are of fine dendritic cell structures with the cell size ranging from 1 to 5μm.The Mg-6Zn-5Ca alloy in RS and annealing(200℃for 1 h) states are mainly composed ofα-Mg,Mg_2Ca,Ca_2Mg_6Zn_3 and a small quantity of Mg_(51)Zn_(20),MgZn_2 and Mg_2Zn_3.Micro-hardness increases with the increment of Ca content and age hardening occurs after aging at 200℃in the flakes probably due to the precipitation strengthening of the fine precipitates Mg_2Ca and Ca_2Mg_6Zn_3.Some phases at the grain boundary in Mg-6Zn-5Ca alloy are identified by means of HRTEM,which may be beneficial to the improvement in thermal stability of the alloy.

On the texture evolution of Mg-Zn-Ca alloy with different hot rolling paths

In the present study,the texture evolution and mechanical anisotropy in a typical Mg–Zn–Ca alloy through hot cross rolling(CR)and unidirectional rolling(UR)were systematically studied.The results show that the rolling path greatly affects the annealed texture.The UR develops a texture with basal poles mainly distributing along the transverse direction(TD).By contrast,an ellipse-like(0002)texture with basal pole inclining largely away from the normal direction(ND)is developed after hot cross rolling and annealing.Therefore,the CR is an effective method to tailor the texture of the experimental alloy.Unfortunately,this ellipse-like texture could not reserve during the subsequent unidirectional hot rolling and annealing.Both UR and CR plates exhibit a strong planar mechanical anisotropy compared with the traditional unidirectional rolled plate.

Surface modification of biomedical Mg-Ca and Mg-Zn-Ca alloys using selective laser melting: Corrosion behaviour, microhardness and biocompatibility

Magnesium alloys such as Mg–Ca and Mg–Zn–Ca are good orthopaedic materials;however their tendency to corrode is high.Herein we utilize selective laser melting(SLM)to modify the surface of these Mg alloys to simultaneously improve the corrosion behaviour and microhardness.The corrosion rate decreased from 2.1±0.2 mm/y to 1.0±0.1 mm/y for the laser-processed Mg–0.6Ca,and from 1.6±0.1 mm/y to 0.7±0.2 mm/y for laser-processed Mg–0.5Zn–0.3Ca.The microhardness increased from 46±1 HV to 56±1 HV for Mg–0.6Ca,and from 47±3 HV to 55±3 HV for Mg–0.5Zn–0.3Ca.In addition,good biocompatibility remained in the laser processed Mg alloys.The improved properties are attributed to laser-induced grain refinement,confined impurity elements,residual stress,and modified surface chemistry.The results demonstrated the potential of SLM as a surface engineering approach for developing advanced biomedical Mg alloys.

Effect of heat treatment on the mechanical and biocorrosion behaviour of two Mg-Zn-Ca alloys

The effect of heat treatment on the mechanical and biocorrosion behaviour of the Mg-1 wt.%Zn-1 wt.%Ca(ZX11)and Mg-3 wt.%Zn-0.4 wt.%Ca(ZX30)alloys was evaluated.For this purpose,three-point bending tests as well as electrochemical and immersion tests in Hank’s solution were performed on both alloys in four different thermal conditions:as-cast,solution-treated,peak-aged and over-aged.Microstructural examinations revealed that the as-cast ZX11 and ZX30 alloys exhibit a microstructure composed ofα-Mg grains separated by large Mg_(2)Ca and Ca_(2)Mg_(6)Zn_(3) particles and by large Ca_(2)Mg_(6)Zn_(3) particles,respectively.During solution treatment,the Ca_(2)Mg_(6)Zn_(3) precipitates at the grain boundaries(GBs)are fully dissolved in the ZX11 alloy,but mainly redistributed to form a more connected configuration in the ZX30 alloy,showing a poor age-hardening response.Consequently,after solution-treatment,galvanic corrosion and corrosion rate decreases in the former,but increases in the latter.The peak-aged condition displays the highest corrosion rate for both alloys,maybe due to an excessive number density of fine Ca_(2)Mg_(6)Zn_(3) particles acting as cathodic sites.However,the over-aged condition shows the lowest corrosion rate for the ZX11 alloy and a very similar one to that of the as-cast sample for the ZX30 alloy.The ZX11 alloy shows generally better biocorrosion behaviour than the ZX30 alloy to its lower content in the Ca_(2)Mg_(6)Zn_(3) phase and thus reduced galvanic corrosion.The Mg_(2)Ca phase present in the studied ZX11 alloy has been proved to exhibit an increased corrosion potential,which has been related to an observed enrichment with Zn.

电流模式对Mg-Zn-Ca镁合金微弧氧化涂层孔隙及耐腐蚀性的影响

分别采用单极、双极和混合电流模式在Mg-Zn-Ca合金基板上制备3种微弧氧化涂层。通过扫描电镜(SEM)和三维激光扫描共聚焦显微镜测量了涂层的孔隙尺寸、表面形貌和表面粗糙度,涂层的物相结构采用X射线衍射仪进行表征,应用电化学工作站和500 h的盐雾腐蚀对3种涂层进行耐腐蚀性研究。结果表明:3种涂层均主要由MgO、Mg_(2)SiO_(4)、Mg_(2)SiO_(3)相组成,混合电流模式下得到的涂层表面光洁度更好,表面气孔尺寸达到(5.52±0.63)μm;同时较小的孔隙形成了屏障阻隔效应,使其耐蚀性高于单极和双极模式涂层的。

Effect of Zn content on microstructure,mechanical properties and thermal conductivity of extruded Mg-Zn-Ca-Mn alloys

Mg-Zn-Ca-Mn series alloys are developed as promising candidates of 5G communication devices with excellent thermal conductivities,great ductility,and acceptable strength.In present paper,Mg-x Zn-0.4Ca-0.2Mn(x=2wt%,4wt%,6wt%)alloys were prepared by a near-solidus extrusion and the effect of Zn content on mechanical and thermal properties were investigated.The results showed that the addition of minor Ca led to the formation of Ca_(2)Mg_(6)Zn_(3) eutectic phase at grain boundaries.A type of bimodal microstructure occurred in the as-extruded alloys,where elongated coarse deformed grains were embedded in refined recrystallized grains matrix.Correspondingly,both yield strength and ductility of the alloys were significantly enhanced after extrusion due to the great grain refinement.Specially,higher Zn content led to the increment in yield strength and a slight reduction in elongation due to the larger fractions of second phase particles.The room temperature thermal conductivity of as-extruded alloys was also improved compared with that of as-cast counterparts.The increment of Zn content decreased the thermal conductivity of both as-cast and as-extruded alloys,which was due to the increased second phase fraction and solution atoms in the matrix,that hindering the motion of electrons.The as-extruded Mg-2Zn-0.4Ca-0.2Mn(wt%)alloy exhibited the highest elongation of 27.7% and thermal conductivity of 139.2 W/(m·K),combined with an acceptable ultimate tensile strength of 244.0 MPa.The present paper provides scientific guidance for the preparation of lightweight materials with high ductility and high thermal conductivity.

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.

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.

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.

Machine learning-assisted efficient design of Cu-based shape memory alloy with specific phase transition temperature

The martensitic transformation temperature is the basis for the application of shape memory alloys(SMAs),and the ability to quickly and accurately predict the transformation temperature of SMAs has very important practical significance.In this work,machine learning(ML)methods were utilized to accelerate the search for shape memory alloys with targeted properties(phase transition temperature).A group of component data was selected to design shape memory alloys using reverse design method from numerous unexplored data.Component modeling and feature modeling were used to predict the phase transition temperature of the shape memory alloys.The experimental results of the shape memory alloys were obtained to verify the effectiveness of the support vector regression(SVR)model.The results show that the machine learning model can obtain target materials more efficiently and pertinently,and realize the accurate and rapid design of shape memory alloys with specific target phase transition temperature.On this basis,the relationship between phase transition temperature and material descriptors is analyzed,and it is proved that the key factors affecting the phase transition temperature of shape memory alloys are based on the strength of the bond energy between atoms.This work provides new ideas for the controllable design and performance optimization of Cu-based shape memory alloys.

Microstructures,corrosion behavior and mechanical properties of as-cast Mg-6Zn-2X(Fe/Cu/Ni)alloys for plugging tool applications

Mg-6Zn-2X(Fe/Cu/Ni)alloys were prepared through semi-continuous casting,with the aim of identifying a degradable magnesium(Mg)alloy suitable for use in fracturing balls.A comparative analysis was conducted to assess the impacts of adding Cu and Ni,which result in finer grains and the formation of galvanic corrosion sites.Scanner electronic microscopy examination revealed that precipitated phases concentrated at grain boundaries,forming a semi-continuous network structure that facilitated corrosion penetration in Mg-6Zn-2Cu and Mg-6Zn-2Ni alloys.Pitting corrosion was observed in Mg-6Zn-2Fe,while galvanic corrosion was identified as the primary mechanism in Mg-6Zn-2Cu and Mg-6Zn-2Ni alloys.Among the tests,the Mg-6Zn-2Ni alloy exhibited the highest corrosion rate(approximately 932.9 mm/a)due to its significant potential difference.Mechanical testing showed that Mg-6Zn-2Ni alloy possessed suitable ultimate compressive strength,making it a potential candidate material for degradable fracturing balls,effectively addressing the challenges of balancing strength and degradation rate in fracturing applications.

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.

Effect of icosahedral phase formation on the stress corrosion cracking(SCC)behaviors of the as-cast Mg-8%Li(in wt.%)based alloys

Through exploring the stress corrosion cracking(SCC)behaviors of the as-cast Mg-8%Li and Mg-8%Li-6%Zn-1.2%Y alloys in a 0.1 M NaCl solution,it revealed that the SCC susceptibility index(I_(SCC))of the Mg-8%Li alloy was 47%,whilst the I_(SCC)of the Mg-8%Li-6%Zn-1.2%Y alloy was 68%.Surface,cross-sectional and fractography observations indicated that for the Mg-8%Li alloy,theα-Mg/β-Li interfaces acted as the preferential crack initiation sites and propagation paths during the SCC process.With regard to the Mg-8%Li-6%Zn-1.2%Y alloy,the crack initiation sites included the I-phase and the interfaces of I-phase/β-Li andα-Mg/β-Li,and the preferential propagation paths were the I-phase/β-Li andα-Mg/β-Li interfaces.Moreover,the SCC of the two alloys was concerned with hydrogen embrittlement(HE)mechanism.