Processing of a Novel Zn Alloy Micro-Tube for Biodegradable Vascular Stent Application

In recent years, zinc based alloys as a new biodegradable metal material aroused intensive interests. However, the processing of Zn alloys micro-tubes （named slender-diameter and thin-walled tubes） is very difficult due to their HCP crystal structure and unfavorable mechanical properties. This study aimed to develop a novel technique to produce micro-tube of Zn alloy with good performance for biodegrad- able vascular stent application. In the present work, a processing method that combined drilling, cold rolling and optimized drawing was proposed to produce the novel Zn-5Mg-1Fe （wt%） alloy micro- tubes. The micro-tube with outer diameter of 2.5 mm and thickness of 130 μm was fabricated by this method and its dimension errors are within 10 μm. The micro-tube exhibits a fine and homogeneous microstructure, and the ultimate tensile strength and ductility are more than 220 MPa and 20% respectively. In addition, the micro-tube and stents of Zn alloy exhibit superior in vitro corrosion and expansion performance. It could be concluded that the novel Zn alloy micro-tube fabricated by above method might be a promising candidate material for biodegradable stent.

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.

Synergistic effect of gradient Zn content and multiscale particles on the mechanical properties of Al-Zn-Mg-Cu alloys with coupling distribution of coarse-fine grains

This study investigated the influence of graded Zn content on the evolution of precipitated and iron-rich phases and grain struc-ture of the alloys,designed and developed the Al–8.0Zn–1.5Mg–1.5Cu–0.2Fe(wt%)alloy with high strength and formability.With the increase of Zn content,forming the coupling distribution of multiscale precipitates and iron-rich phases with a reasonable matching ratio and dispersion distribution characteristics is easy.This phenomenon induces the formation of cell-like structures with alternate distribu-tion of coarse and fine grains,and the average plasticity–strain ratio(characterizing the formability)of the pre-aged alloy with a high strength is up to 0.708.Results reveal the evolution and influence mechanisms of multiscale second-phase particles and the corresponding high formability mechanism of the alloys.The developed coupling control process exhibits considerable potential,revealing remarkable improvements in the room temperature formability of high-strength Al–Zn–Mg–Cu alloys.

Machine learning design of 400 MPa grade biodegradable Zn-Mn based alloys with appropriate corrosion rates

The commonly used trial-and-error method of biodegradable Zn alloys is costly and blindness.In this study,based on the self-built database of biodegradable Zn alloys,two machine learning models are established by the first time to predict the ultimate tensile strength(UTS)and immersion corrosion rate(CR)of biodegradable Zn alloys.A real-time visualization interface has been established to design Zn-Mn based alloys;a representative alloy is Zn-0.4Mn-0.4Li-0.05Mg.Through tensile mechanical properties and immersion corrosion rate tests,its UTS reaches 420 MPa,and the prediction error is only 0.95%.CR is 73μm/a and the prediction error is 5.5%,which elevates 50 MPa grade of UTS and owns appropriate corrosion rate.Finally,influences of the selected features on UTS and CR are discussed in detail.The combined application of UTS and CR model provides a new strategy for synergistically regulating comprehens-ive properties of biodegradable Zn alloys.

Structural,mechanical and electronic properties of precipitates in Mg−Zn alloys

To accelerate the development and design of magnesium(Mg)alloys,the structural and mechanical properties of important precipitates in Mg−Zn alloys were studied by experiments and density functional theory.The nano-indentation tests revealed that the hardness of the precipitates initially increased and then decreased with increasing Zn content,and was significantly higher than that of pure Mg and Zn.The calculation results revealed that the precipitates stability initially increased and then decreased with increasing Zn concentration.The bulk moduli of the precipitates increased,whereas their shear and Young’s moduli initially increased and then decreased with increasing Zn content.The decreasing order of ductility for these compounds is MgZn_(2)>Mg_(21)Zn_(25)>Mg_(2)Zn_(11)>Mg_(4)Zn_(7).The surface profiles of the compounds revealed that they are obvious anisotropy.Both the degree of covalency and bond length of covalent bonds initially increased and then decreased with increasing Zn content.

Effect of cold rolling deformation on microstructure evolution and mechanical properties of spray formed Al−Zn−Mg−Cu−Cr alloys

The impact of cold rolling deformation,which was introduced after solid solution and before aging treatment,on microstructure evolution and mechanical properties of the as-extruded spray formed Al−9.8Zn−2.3Mg−1.73Cu−0.13Cr(wt.%)alloy,was investigated.SEM,TEM,and EBSD were used to analyze the microstructures,and tensile tests were conducted to assess mechanical properties.The results indicate that the D1-T6 sample,subjected to 25%cold rolling deformation,exhibits finer grains(3.35μm)compared to the D0-T6 sample(grain size of 4.23μm)without cold rolling.Cold rolling refines the grains that grow in solution treatment.Due to the combined effects of finer and more dispersed precipitates,higher dislocation density and smaller grains,the yield strength and ultimate tensile strength of the D1-T6 sample can reach 663 and 737 MPa,respectively.In comparison to the as-extruded and D0-T6 samples,the yield strength of the D1-T6 sample increases by 415 and 92 MPa,respectively.

Improvement of microstructure and mechanical properties of Al−Cu−Li−Mg−Zn alloys through water-cooling centrifugal casting technique

The microstructure and mechanical properties of as-cast Al−Cu−Li−Mg−Zn alloys fabricated by conventional gravity casting and centrifugal casting techniques combined with rapid solidification were investigated.Experimental results demonstrated that compared with the gravity casting technique,the water-cooling centrifugal casting technique significantly reduces porosity,refinesα(Al)grains and secondary phases,modifies the morphology of secondary phases,and mitigates both macro-and micro-segregation.These improvements arise from the synergistic effects of the vigorous backflow,centrifugal field,vibration and rapid solidification.Porosity and coarse plate-like Al13Fe4/Al7Cu2Fe phase result in the fracture before the gravity-cast alloy reaches the yield point.The centrifugal-cast alloy,however,exhibits an ultra-high yield strength of 292.0 MPa and a moderate elongation of 6.1%.This high yield strength is attributed to solid solution strengthening(SSS)of 225.3 MPa,and grain boundary strengthening(GBS)of 35.7 MPa.Li contributes the most to SSS with a scaling factor of 7.9 MPa·wt.%^(-1).The elongation of the centrifugal-cast alloy can be effectively enhanced by reducing the porosity and segregation behavior,refining the microstructure and changing the morphology of secondary phases.

Microstructure evolution and mechanical properties of Mg-x%Zn-1%Mn(x=4,5,6,7,8,9) wrought magnesium alloys

The roles of Zn content and thermo-mechanical treatment in affecting microstructures and mechanical properties of Mg-x%Zn-1%Mn（mass fraction,x=4,5,6,7,8,9） wrought Mg alloys were investigated.The microstructure was extremely refined by dynamic recrystallization（DRC） during extrusion.With increasing Zn content,the DRC grains tended to grow up,at the same time,more second phase streamlines would be present,which restricted the further growing.During solution treatment,the DRC grains would rapidly grow up;however,higher Zn content could hinder the grain boundary expanding,which results in finer ultimate grains.MgZn2 dispersoid particles which are coherent with the matrix would precipitate from the supersaturated solid solution during the one-step aging process,and nano-sized GP zones formed during the pre-aging stage of the two-step aging provide a huge amount of effective nuclei for the MgZn2 phases formed in the second stage,which makes the MgZn2 particles much finer and more dispersed.The mechanical properties of as-extruded samples were not so sensitive to the variation of Zn content,the tensile strength fluctuates between 300 and 320 MPa,and the elongation maintains a high value between 11% and 14%.The strength of aged samples rises as a parabolic curve with increasing Zn content,specifically,the tensile strength of one-step aged samples rises from 278 to 374 MPa,and that of two-step aged ones rises from 284 to 378 MPa,yet the elongation of all aged samples is below 8%.When Zn content exceeds its solid solution limit in Mg-Zn system（6.2%,mass fraction）,the strength rises slowly but the elongation deteriorates sharply,so a Mg-Zn-Mn alloy with 6% Zn possesses the best mechanical properties,that is,the tensile strengths after one-and two-step aging are 352 and 366 MPa,respectively,and the corresponding elongations are 7.98% and 5.2%,respectively.

Microstructure of 18R-type long period ordered structure phase in Mg_(97)Y_2Zn_1 alloy

The microstructure of the 18R-type long period stacking ordered （LPSO） phase in Mg 97 Y 2 Zn 1 alloy was investigated by the first principles calculation. The arrangement rule of Zn and Y atoms in the LPSO structure is determined theoretically. The calculation results reveal that the additive atoms are firstly located in the fault layers at the two ends of the 18R-type LPSO structure, and then extend to fault layers in the interior, which is in good agreement with the experimental observations. This feature also implies the microstructural relationship between 18R and other LPSO structures. The cohesive energy and the formation heat indicate the dependence of the stability of 18R LPSO structure on contents of Y and Zn atoms. The calculated electronic structures reveal the underlying mechanism of microstructure and the stability of 18R LPSO structure.

In vitro and in vivo evaluation of effects of Mg-6Zn alloy on tight junction of intestinal epithelial cell

The effects of biodegradable Mg?6Zn alloy on tight junction of intestinal epithelial cells (IEC-6) were investigated. In the in vitro experiments, the cells were exposed to Mg?6Zn alloy extracts with different concentrations (0, 20% and 40%) for 1, 3 and 5 d. The real-time polymerase chain reaction (PCR) results show that when the cells are treated with 40% and 20% extracts, the expression of Zona Occludens 1 (ZO-1) and Occludin increase as compared with those in the control group. In the in vivo experiments, Mg?6Zn alloy and titanium staples were implanted into rabbits’ intestinal tract for 1, 2 and 3 weeks. By immunohistochemical staining of peri-implant intestinal tissue, increased expression of Occludin and ZO-1 are observed in the Mg?6Zn alloy groups as compared with those in the titanium and control groups. The results show that Mg?6Zn alloy in intestine may promote the regeneration of tight junction, and the extract with a certain concentration can induce the expression of tight junction related genes in IEC-6 cells.

Microstructure and mechanical properties of Mg_(94)Zn_2Y_4 extruded alloy with long-period stacking ordered structure

The microstructure and mechanical properties of Mg94Zn2Y4 extruded alloy containing long-period stacking ordered structures were systematically investigated by SEM and TEM analyses. The results show that the 18R-LPSO structure and α-Mg phase are observed in cast Mg94Zn2Y4 alloy. After extrusion, the LPSO structures are delaminated and Mg-slices with width of 50-200 nm are generated. By ageing at 498 K for 36 h, the ageing peak is attained andβ′phase is precipitated. Due to this novel precipitation, the microhardness ofα-Mg matrix increases apparently from HV108.9 to HV129.7. While the microhardness for LPSO structure is stabilized at about HV145. TEM observations and SAED patterns indicate that the β′ phase has unique orientation relationships betweenα-Mg and LPSO structures, the direction in the close-packed planes ofβ′precipitates perpendicular to that ofα-Mg and LPSO structures. The ultimate tensile strength for the peak-aged alloy achieves 410.7 MPa and the significant strength originates from the coexistence ofβ′precipitates and 18R-LPSO structures.

Molecular dynamics simulation of relationship between local structure and dynamics during glass transition of Mg_7Zn_3 alloy

The rapid solidification process of Mg7Zn3 alloy was simulated by the molecular dynamics method. The relationship between the local structure and the dynamics during the liquid-glass transition was deeply investigated. It was found that the Mg-centered FK polyhedron and the Zn-centered icosahedron play a critical role in the formation of Mg7Zn3 metallic glass. The self-diffusion coefficients of Mg and Zn atoms deviate from the Arrhenius law near the melting temperature and then satisfy the power law. According to the time correlation functions of mean-square displacement, incoherent intermediate scattering function and non-Gaussian parameter, it was found that the β-relaxation in Mg7Zn3 supercooled liquid becomes more and more evident with decreasing temperature, and the α-relaxation time rapidly increases in the VFT law. Moreover, the smaller Zn atom has a faster relaxation behavior than the Mg atom. Some local atomic structures with short-range order have lower mobility, and they play a critical role in the appearance of cage effect in theβ-relaxation regime. The dynamics deviates from the Arrhenius law just at the temperature as the number of local atomic structures begins to rapidly increase. The dynamic glass transition temperature （Tc） is close to the glass transition point in structure （TgStr）.

Microstructure of Mg-8Zn-4Al-1Ca aged alloy

The microstructure of Mg-8Zn-4Al-1Ca aged alloy was investigated by TEM and HRTEM. The results show that the hardening produced in the Mg-8Zn-4Al-1Ca alloy is considerably higher than that in the Mg-8Zn-4A1 alloy. A dense dispersion of disc-like Ca2Mg6Zn3 precipitates are formed in Mg-8Zn-4Al-1Ca alloy aged at 160 ℃ for 16 h. In addition, the lattice distortions, honeycomb-looking Moir＆#233; fringes, edge dislocations and dislocation loop also exist in the microstructure. The precipitates of alloy aged at 160 ℃ for 48 h are coarse disc-like and fine dispersed grainy. When the alloy is subjected to aging at 160 ℃ for 227 h, the microstructure consists of numerous MgZn2 precipitates and Ca2Mg6Zn3 precipitates. All the analyses show that Ca is a particularly effective trace addition in improving the age-hardening and postponing the formation of MgZn2 precipitates in Mg-8Zn-4Al alloy aged at 160 ℃.

TEM microstructure of rapidly solidified Mg-6Zn-1Y-1Ce alloy

Rapidly solidified（RS） Mg-6Zn-1Y-1Ce ribbons were prepared by single roller melt-spinning technique.Transmission electron microscopy and energy dispersive X-ray spectroscopy were employed to characterize the microstructure of RS ribbons.The results show that there is high density of particles distributed within grains and at grain boundaries in the region near wheel side.The particle density is decreased in the middle region and free surface region.The alloy is predominantly composed of supersaturated--Mg solid solution,T phase and W phase;meanwhile,a few icosahedral quasicrystalline and Mg4Zn7 particles are also observed.The T phase is confirmed having a body-centered orthorhombic structure that is transformed from the body-centered tetragonal structure Mg12Ce phase due to the partial substitution of Mg atoms by Zn.

不同预时效挤压态Mg−Gd−Y−Zn−Zr合金的再结晶行为和强化机制

通过控制预时效时间制备3种不同状态的试样,研究不同预时效状态对挤压态Mg−9.5Gd−4Y−2.2Zn−0.5Zr(质量分数,%)合金的动态再结晶行为(DRX)和性能的影响。结果表明,欠时效挤压(UAE)样品的细晶体积分数为17.4%,而峰时效挤压(PAE)和过时效挤压(OAE)样品的细晶体积分数分别达到89.7%和50.4%。在晶粒内部和晶界处分布的致密、细小的β颗粒相通过粒子激发形核机制显著提高了形核位点和位错密度。然而,致密针状γ'相抑制位错滑移,延迟DRX形核。PEA和OAE样品中细小晶粒的差异归因于原始颗粒相的数量和尺寸的不同,而其拉伸性能的差异归因于不同的显微组织。由于晶界强化和析出强化机制的贡献更大,PAE样品具有更优异的拉伸性能。

生物可降解挤压态Mg-Sn-Zn-Zr合金组织与腐蚀性能的研究

采用气体保护法制备了高强塑性Mg-Sn-Zn-Zr(TZK)合金,然后在不同温度(300、350、400℃)对其进行挤压变形,并对合金的微观组织、物相组成和体外降解行为进行研究。结果表明:300℃挤压后合金的组织为均匀细小的等轴晶,晶粒尺寸最小,为6.57μm;析氢量和腐蚀速率最低,耐腐蚀性能最好。随挤压温度升高,合金的晶粒长大,组织中出现孪晶,导致其耐腐蚀性能变差。

超声处理对可降解Zn-0.5Sr合金组织及腐蚀性能的影响

以Zn-0.5Sr合金为对象,研究了不同超声功率(0、300、600、900 W)对Zn-0.5Sr合金显微组织及腐蚀性能的影响.结果表明:Zn-0.5Sr合金经过超声处理后,铸态组织中SrZn13相由粗大的多边形转变为细小的块状,与未处理的合金相比较,对合金进行600 W超声处理后,合金的电化学腐蚀速率由2.078±0.141 mm/a增加至5.747±0.390 mm/a.当超声功率为600 W时,Zn-0.5Sr合金15、30 d的浸泡腐蚀速度分别为0.090±0.0021、0.074±0.0019 mm/a,是未经超声处理的1.88、1.95倍.

通过不同热挤压方式制备具有较优强塑性组合的新型Mg-5Sn-2Al-1Zn合金

制备新型Mg-5Sn-2Al-1Zn(TAZ521)合金。为提高合金的强度与塑性,采用正挤压(DE)和挤压-剪切(ES)两种工艺对该合金进行变形处理。通过XRD、SEM、TEM、EBSD和拉伸试验等方法研究均匀态和挤压态合金的显微组织演变、织构演变及强化机制。结果表明,正挤压态合金的力学性能得到改善;然而,合金表现出由粗晶和细小动态再结晶(DRXed)晶粒组成的双峰组织。经过挤压-剪切变形后的合金组织变得更加均匀,并且实现更好的强韧性结合,变形后合金的屈服强度(YS)、极限抗拉强度(UTS)和伸长率(EL)分别达到212 MPa、303 MPa和21.7%。晶粒细化和Mg2Sn析出物的钉扎效应对强度的提高起到重要作用,此外,延展性的提高归因于基面纤维织构的弱化和非基面滑移系的激活。

Effects of heat treatment on microstructure and mechanical properties of Mg-5Zn-0.63Er alloy

The microstructure evolution of the Mg 5Zn 0.63Er（mass fraction,%） alloy containing quasicrystalline phase（I-phase） under the as-cast condition was investigated via different heat treatments.The results show that apart from the precipitation of the W-phase particles,the I-phase almost dissolves into the matrix after solid solution treatment at 480℃ for 10 h（T4 state）.The solution-treated alloy was aged at 175℃ for 6-100 h（T6 state）.The ultimate tensile strength of the peak-aged alloy is approximately 261 MPa companying with an elongation of 10.5%.The improvement of the tensile strength is mainly attributed to the presence of the rod-like MgZn 2 particles.

电弧喷涂Zn-Al伪合金涂层耐腐蚀性能研究进展

通过在钢基体表面制备涂层可以很好地延长钢铁材料的服役时间,减少因腐蚀造成的重大事故和人员伤亡。相较于传统的纯Zn涂层、纯Al涂层以及Zn-Al合金涂层,Zn-Al伪合金涂层能够为基体材料提供长久有效的腐蚀防护,在钢铁材料的腐蚀防护中具有巨大的应用潜力。简述了Zn-Al伪合金涂层电弧喷涂制备工艺的特点;介绍了Zn、Al、Zn-Al合金及Zn-Al伪合金涂层在模拟海洋环境下的腐蚀防护原理;在此基础上从组分、喷涂工艺参数(喷涂距离、喷涂电流和喷涂电压)、元素掺杂(Mg、Si及Re)及后处理工艺(封孔、激光重熔)等角度,论述了其对Zn-Al伪合金涂层耐蚀性的影响;讨论了Zn-Al伪合金涂层防腐体系在桥梁、海洋钢结构件、地下运输管道中的应用现状;最后总结了目前研究工作中存在的挑战,提出了电弧喷涂Zn-Al伪合金涂层尚需深入研究的重点问题,为提高钢铁材料使用寿命提供了参考。