In vitro performance of a biodegradable zinc alloy adjustable-loop cortical suspension fixation for anterior cruciate ligament reconstruction

Anterior cruciate ligament(ACL)injuries of the knee are one of the most common and serious athletic injuries.The widely used cortical suspension fixation buttons for ligament reconstruction are permanent implants,particularly those made from conventional steel or titanium alloys.In this study,a biodegradable Zn-0.45Mn-0.2Mg(ZMM42)alloy with the yield strength of 300.4 MPa and tensile strength of 329.8 MPa was prepared through hot extrusion.The use of zinc alloys in the preparation of cortical suspension fixation buttons was proposed for the first time.After 35 d of immersion in simulated body fluids,the ZMM42 alloy fixation buttons were degraded at a rate of 44μm/a,and the fixation strength was retained(379.55 N)in the traction loops.Simultaneously,the ZMM42 alloy fixation buttons exhibited an increase in MC3T3-E1 cell viability and high antibacterial activity against Escherichia coli and Staphylococcus aureus.These results reveal the potential of biodegradable zinc alloys for use as ligament reconstruction materials and for developing diverse zinc alloy cortical suspension fixation devices.

Stable anode-free zinc-ion batteries enabled by alloy network-modulated zinc deposition interface

Newly-proposed anode-free zinc-ion batteries(ZIBs)are promising to remarkably enhance the energy density of ZIBs,but are restricted by the unfavorable zinc deposition interface that causes poor cycling stability.Herein,we report a Cu-Zn alloy network-modulated zinc deposition interface to achieve stable anode-free ZIBs.The alloy network can not only stabilize the zinc deposition interface by suppressing 2D diffusion and corrosion reactions but also enhance zinc plating/stripping kinetics by accelerating zinc desolvation and nucleation processes.Consequently,the alloy network-modulated zinc deposition interface realizes high coulombic efficiency of 99.2%and high stability.As proof,Zn//Zn symmetric cells with the alloy network-modulated zinc deposition interface present long operation lifetimes of 1900 h at 1 m A/cm^(2)and 1200 h at 5 m A/cm^(2),significantly superior to Zn//Zn symmetric cells with unmodified zinc deposition interface(whose operation lifetime is shorter than 50 h),and meanwhile,Zn3V3O8cathodebased ZIBs with the alloy network-modified zinc anodes show notably enhanced rate capability and cycling performance than ZIBs with bare zinc anodes.As expected,the alloy network-modulated zinc deposition interface enables anode-free ZIBs with Zn3V3O8cathodes to deliver superior cycling stability,better than most currently-reported anode-free ZIBs.This work provides new thinking in constructing high-performance anode-free ZIBs and promotes the development of ZIBs.

Effectiveness Evaluation Study of Self-made Zinc Alloy Sacrificial Anode under Chloride Salt Erosion Environment

To investigate the effectiveness of self-made zinc alloy sacrificial anode material for the protection of reinforcement in concrete under chlorine salt erosion environment,salt solution immersion corrosion and electromigration accelerated corrosion tests were used to evaluate the effectiveness of self-made zinc alloy anode with the help of relevant cathodic protection guidelines and evaluation criteria for the corrosion of reinforcement in concrete.The results showed that the protection was effective because the potential of the zinc alloy anode protection steel bar in the salt solution satis?ed the“-780 mV(SCE)”validity criterion.The self-corrosion potential(E_(corr))of the sacri?cial anode protection steel in concrete was greater than-276 mV,and the protective current density of the zinc alloy anode was 1-3μA·cm^(-2),which met the standards of EN12696-2000,further indicating that the self-made zinc alloy sacri?cial anode had a good protection combining with the polarization resistance and the appearance of the corroded surface of the steel in concrete.The microscopic morphology of the corroded surface and the composition of the corrosion products indicates that the mortar of the self-made zinc alloy anode has a lower pH than the imported anodes,so the long-term protection of the selfmade zinc alloy sacri?cial anode needs to be further improved.

Investigation and improvement of tiny spot defects on hot-dip galvanized automotive steel sheets

The causes of tiny spot defects on the surface of hot-dip galvanized automotive steel sheets were studied using scanning electron microscopy(SEM)and energy dispersive spectrometer(EDS),and effective control measures were introduced.The results show that rubbing against the top roller after galvanizing is easy due to the local thickness of tiny spot defect location coating;therefore,the surface morphology is different from the normal part.Three kinds of defects,namely zinc slag,small slivers,and pitting,are likely to cause local thickening of the coating after galvanizing,leading to the formation of tiny spots.Therefore,resolving the three types of defects can effectively control the generation of tiny spot defects.Among them,due to the hereditary nature of the small sliver defect,focusing on its control and supervision is necessary.

Corrosion resistance of cerium-doped zinc calcium phosphate chemical conversion coatings on AZ31 magnesium alloy

Zinc calcium phosphate （Zn-Ca-P） coating and cerium-doped zinc calcium phosphate （Zn-Ca-Ce-P） coating were prepared on AZ31 magnesium alloy. The chemical compositions, morphologies and corrosion resistance of coatings were investigated through energy-dispersive X-ray spectroscopy （EDS）, X-ray photoelectron spectroscopy （XPS）, X-ray diffraction （XRD）, electron probe micro-analysis （EPMA） and scanning electron microscopy （SEM） together with hydrogen volumetric and electrochemical tests. The results indicate that both coatings predominately contain crystalline hopeite （Zn3（PO4）2·4H2O）, Mg3（PO4）2 and Ca3（PO4）2, and traces of non-crystalline MgF2 and CaF2. The Zn-Ca-Ce-P coating is more compact than the Zn-Ca-P coating due to the formation of CePO4, and displays better corrosion resistance than the Zn-Ca-P coating. Both coatings protect the AZ31 Mg substrate only during an initial immersion period. The micro-galvanic corrosion between the coatings and their substrates leads to an increase of hydrogen evolution rate （HER） with extending the immersion time. The addition of Ce promotes the homogenous distribution of Ca and formation of hopeite. The Zn-Ca-Ce-P coating has the potential for the primer coating on magnesium alloys.

EIS studies the effect of Zinc to Al-Zn alloy used for cathodic protection in 3% NaCl solution

Electrochemical impendence spectroscopy （EIS） is applied to investigate the dissolution behavior of Al-Zn alloys in 3% NaCl solution at different polarization potentials. A new reaction model is proposed, and the activation mechanism of zinc in Al-Zn alloys is achieved. There are three intermediates in the dissolution process： Znad^＋, Znad^2＋ and Alad^＋, ,of which only Zni can activate Al-Zn alloys. Most Znnd^＋ is produced by β-phase,and the alloys with 2. 3% - 3. 8% （wt） Zn dissolve rapidly. The Al-Zn alloys of heart-shaped EIS are active in 3% NaCl solution, thus EIS characteristic can be used to distinguish the activa-tion of Al-Zn alloys.

Effect of zinc addition on microstructure and mechanical properties of Mg-7Y-3Sm-0.5Zr alloy

The effect of zinc addition on the microstructure and mechanical properties of Mg-7Y-3Sm-0.5Zr casting alloy was investigated. Creep test was carried out at 200-300 °C under 50-120 MPa. Within the limits of the creep test conditions used in this study, the creep activation energy of the investigated alloys was in the range of 156-221 kJ/mol. The microstructure evolution during creep was characterized by optical metallography, SEM and TEM. The results show that the creep life of the alloy is increased from 52.2 to 152.8 h at 300 °C under 50 MPa by only 1% addition of Zn, though both the alloys have similar creep behaviors below 250 °C, which suggests that the thermally stable compound and lamellar structure can improve the high temperature creep resistance of the alloy with the addition of Zn.

MICROSTRUCTURES OF A NOVEL HIGH STRENGTH AND WEAR-RESISTING ZINC ALLOY

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Isothermal corrosion Fe_3Si alloy in liquid zinc

The isothermal corrosion testing, microscopic examination and the performance of Fe3Si alloy as materials of construction for bath hardware in continuous hot-dipping lines were studied. The corrosion of Fe3Si alloy in molten zinc was controlled by attacking the grain boundaries preferentially. Aluminum reacted with iron of Fe3Si alloy firstly while the samples were immersed in molten zinc, although aluminum contents in the molten zinc were very low. The phase of reaction product was thought to be Fe2Al5. The corrosion rate of the Fe3Si alloy in molten zinc was determined to be approximately 2.9×10^-3 mm/h, therefore the liquid zinc corrosion resistance of Fe3Si alloy was very weak.

Effect of cooling ways on properties of Al/Pb-0.2%Ag rolled alloy for zinc electrowinning

In order to study the new anode materials for zinc electrowinning,Al/Pb?0.2%Ag rolled alloy was produced by composite casting and hot rolling.Then the effect of cooling ways on properties of Al/Pb?0.2%Ag rolled alloy was investigated.As the results of metallographic test indicated,with the increasing of cooling intensity,both Vickers hardness and yield strength of Al/Pb?0.2%Ag rolled alloy increase.Furthermore,the Al/Pb?0.2%Ag rolled alloy,cooled by ice salt,presents the finest grain size and shows the lowest oxygen evolution potential(1.5902V),while that of alloy cooled by water and air are1.6143V and1.6288V,respectively.However,the corrosion current density and corrosion rate of the Al/Pb?0.2%Ag rolled alloy,cooled by ice salt,are the highest.This can be attributed to its largest specific surface area,which promotes the contact between the anode and electrolyte.

Shot noise analysis on corrosion behavior of zinc alloy (ZnAl4Cul) under dry-wet cycles

The corrosion behaviors of zinc alloy （ZnAl4Cul） in 3.5% （mass fraction） NaCl, 7.3% （mass fraction） Na2SO4 and simulated acid rain solutions were investigated using electrochemical measurements. The potential noise during dry-wet cycle was monitored and analyzed by fast Fourier transform （FFT）, fast wavelet transform （FWT）, shot noise theory and stochastic theory. Cumulative probability curves of event frequency fn indicate that the corrosion events in the dry cycles are greater than those in the wet cycles. Uniform corrosion was observed in the NaCl solution compared with more localized corrosion in the Na2SO4 solution, which is evidenced by FWT and SEM. Conditional events generation rate r（t） for diffusion controlled reactions decreases with increasing the time. r（t） values for uniform corrosion and diffusion controlled process are the largest in the wet cycle in 3.5% NaCl solution. The values of r（t） for pitting corrosion in Na2SO4 solution are observed to become large during spraying periods, and r（t） for pitting corrosion has the largest value in the Na2SO4 solution. The intergranular corrosion of zinc is serious in simulated acid rain solution.

Fast ion diffusion alloy layer facilitating 3D mesh substrate for dendrite-free zinc-ion hybrid capacitors

Although aqueous zinc ion hybrid capacitors have advantageous integration of batteries and supercapacitors,they still suffer from the inherent problems of dendrite growth and interfacial side reactions on Zn anodes.Herein,a universal fast zinc-ion diffusion layer on a three-dimensional(3 D)mesh structure model is demonstrated to effectively improve Zn plating/stripping reversibility.The fast ion diffusion alloy layer accelerates the Zn^(2+)migration in an orderly manner to homogenize Zn^(2+)flux and overcomes the defects of the commercial mesh substrate,effectively avoiding dendrite growth and side reactions.Consequently,the proof-of-concept silver-zinc alloy modified stainless steel mesh delivers superb reversibility with the high coulombic efficiency over 99.4%at 4 mA cm^(-2)after 1600 cycles and excellent reliability of over 830 h at 1 mA cm^(-2),Its feasibility is also evidenced in commercial zinc ion hybrid capacitors with activated carbon as the cathode.This work enriches the fundamental comprehension of fast zinc-ion diffusion layer combined with a 3 D substrate on the Zn deposition and opens a universal approach to design advanced host for Zn electrodes in zinc ion hybrid capacitors.

Novel zinc alloys for biodegradable surgical staples

BACKGROUND The development of biodegradable surgical staples is desirable as non-biodegradable Ti alloy staples reside in the human body long after wound healing, which can cause allergic/foreign-body reactions, adhesion, or other adverse effects. In order to develop a biodegradable alloy suitable for the fabrication of surgical staples, we hypothesized that Zn, a known biodegradable metal, could be alloyed with various elements to improve the mechanical properties while retaining biodegradability and biocompatibility. Considering their biocompatibility, Mg, Ca, Mn, and Cu were selected as candidate alloying elements, alongside Ti, the main material of clinically available surgical staples.AIM To investigate the in vitro mechanical properties and degradation behavior and in vivo safety and feasibility of biodegradable Zn alloy staples.METHODS Tensile and bending tests were conducted to evaluate the mechanical properties of binary Zn alloys with 0.1–6 wt.% Mg, Ca, Mn, Cu, or Ti. Based on the results,three promising Zn alloy compositions were devised for staple applications(wt.%): Zn-1.0Cu-0.2Mn-0.1Ti(Zn alloy 1), Zn-1.0Mn-0.1Ti(Zn alloy 2), and Zn-1.0Cu-0.1Ti(Zn alloy 3). Immersion tests were performed at 37℃ for 4 wk using fed-state simulated intestinal fluid(Fe SSIF) and Hank’s balanced salt solution(HBSS). The corrosion rate was estimated from the weight loss of staples during immersion. Nine rabbits were subjected to gastric resection using each Zn alloy staple, and a clinically available Ti staple was used for another group of nine rabbits. Three in each group were sacrificed at 1, 4, and 12 wk post-operation.RESULTS Additions of ≤1 wt.% Mn or Cu and 0.1 wt.% Ti improved the yield strength without excessive deterioration of elongation or bendability. Immersion tests revealed no gas evolution or staple fracture in any of the Zn alloy staples. The corrosion rates of Zn alloy staples 1, 2, and 3 were 0.02 mm/year in HBSS and 0.12, 0.11, and 0.13 mm/year, respectively, in Fe SSIF. These degradation times are sufficient for wound healing. The degradation rate is notably increased under low pH conditions. Scanning electron microscopy and energy dispersive spectrometry surface analyses of the staples after immersion indicated that the component elements eluted as ions in Fe SSIF, whereas corrosion products were produced in HBSS, inhibiting Zn dissolution. In the animal study, none of the Zn alloy staples caused technical failure, and all rabbits survived without complications. Histopathological analysis revealed no severe inflammatory reaction around the Zn alloy staples.CONCLUSION Staples made of Zn-1.0Cu-0.2Mn-0.1Ti, Zn-1.0Mn-0.1Ti, and Zn-1.0Cu-0.1Ti exhibit acceptable in vitro mechanical properties, proper degradation behavior,and in vivo safety and feasibility. They are promising candidates for biodegradable staples.

Effect of Cu addition on microstructure and properties of Mg-10Zn-5Al-0.1Sb high zinc magnesium alloy

To improve the strength, hardness and heat resistance of Mg-Zn based alloys, the effects of Cu addition on the as-cast microstructure and mechanical properties of Mg-10Zn-5Al-0.1Sb high zinc magnesium alloy were investigated by means of Brinell hardness measurement, scanning electron microscopy （SEM）, energy dispersive spectroscopy （EDS）, XRD and tensile tests at room and elevated temperatures. The results show that the microstructure of as-cast Mg-10Zn-5AI-0.1Sb alloy is composed of α-Mg, τ-Mg32（Al, Zn）49, Ф-Al2MgsZn2 and Mg3Sb2 phases. The morphologies of these phases in the Cu-containing alloys change from semi-continuous long strip to black herringbone as well as particle-like shapes with increasing Cu content. When the addition of Cu is over 1.0wt.%, the formation of a new thermally-stable Mg2Cu phase can be observed. The Brinell hardness, room temperature and elevated temperature strengths firstly increase and then decrease as the Cu content increases. Among the Cucontaining alloys, the alloy with the addition of 2.0wt.% Cu exhibits the optimum mechanical properties. Its hardness and strengths at room and elevated temperatures are 79.35 HB, 190 MPa and 160 MPa, which are increased by 9.65%, 21.1% and 14.3%, respectively compared with those of the Cu-free one. After T6 heat treatment, the strengths at room and elevated temperatures are improved by 20% and 10%, respectively compared with those of the ascast alloy. This research results provide a new way for strengthening of magnesium alloys at room and elevated temperatures, and a method of producing thermally-stable Mg-10Zn-5Al based high zinc magnesium alloys.

Phase selection of ternary intermetallic compounds during solidification of high zinc magnesium alloy

The phase selection of ternary intermetallic compound τphase (Mg32(Al, Zn)49 ) and φ phase (Al2Mg5Zn2) in high zinc magnesium alloys was studied by using scanning electron microscope, X-ray diffractometer and differential scanning calorimeter, etc. The results indicate that, when adding element Si in Mg-8Zn-4Al-0.3Mn (ZA84) alloy, φ phase is promoted, whereas τ phase is inhibited. The Chinese script-type Mg2Si and matrix microstructure are greatly refined, the formation of τ phase is facilitated and φ phase is restrained when modifier Al-AlP master alloy is added in ZA84 alloy containing Si. The kinetics study of phase selection indicates that there is a critical degree of undercooling of the melt. If the undercooling exceeds the critical value, τ phase preferentially forms while φ phase is restrained; otherwise, φ phase preferentially forms while τ phase is restrained.

Strength properties examination of high zinc aluminium alloys inoculated with Ti addition

This paper includes studies on the influence of grain refinement treatment with respect to the composition and structure of high zinc aluminium casting alloys on the changes of their tensile properties. The Al-20 wt.%Zn alloy was inoculated with master alloys Al Ti5B1 and Al Ti3C0.15 to determine the impact of a variable titanium addition on the tensile properties of Al Zn20 alloy, and determine on this basis an optimal addition of Ti that would ensure the improvement of elongation of alloys cast in the sand mould, at the same time maintaining high tensile strength. Within the studies, light microscopy(LM) and strength tests were applied. Experimental results showed that the inoculation of high zinc aluminium alloy Al Zn20 with the master alloys Al Ti5B1 and Al Ti3C0.15 causes intensive structure refinement, while the intensity of reaction of both master alloys is comparable. The Al Ti3C0.15 master alloy addition, selected for further studies, introducing about 100 ppm Ti, enhances the tensile properties of the alloy; the elongation increases about 20% and tensile strength increases about 10% against the initial values(uninoculated alloy). Further increase of the Ti addition up to 500–600 ppm leads to the "overinoculation" effect that is accompanied by the decrease of elongation. Therefore,the Ti addition should be reduced to the level of about 100 ppm which ensures obtaining a set of optimal properties.

Slurry wear characteristics of zinc-based alloys： Effects of sand content of slurry, silicon addition to alloy system and traversal distance

这调查处理在泥浆上与标本和泥浆作文以及遍历距离的效果相关的观察穿基于锌的合金的反应。合金的作文被把 4% 硅加到它改变。泥浆作文通过在被推迟在的 060% 的范围改变沙粒子的集中被改变(液体) 电解质。电解质包含了集中的硫的酸在水的 10 L 溶解了的 4 g 钠氯化物和 5 mL。泥浆穿测试在 15500 km 的遍历距离范围上以 7.02 m/s 的速度被进行。wear 率开始与遍历距离增加了，达到了最大值并且不管标本和测试环境，此后减少了。然而， wear 率山峰比液体唯一的媒介在加沙环境的液体是不太突出的。进一步，在液体唯一的媒介的 wear 率山峰在包含泥浆的沙比那座出现在更短的遍历距离。到电解质的沙粒子的增加把样品的 wear 率归结为取决于泥浆的沙集中的 5%15% 。而且，中介(40%) 沙内容导致了最大值穿率什么时候与相比在加沙媒介的液体。然而，这最大值是静止的不到在里面液体唯一的媒介。包含更高受不了的合金的硅比当在液体唯一的媒介测试了时，免费合金取样的硅穿率。相反，而混合回答在包含 60% 沙的泥浆被注意，趋势加 20% 和 40% 沙环境在液体逆行。在后者盒子中，当一个相反的趋势在更长的遍历距离被观察时，硅的存在开始证明有害。样品的 wear 反应在试验性的条件的一个给定的集合以他们象硅和占优势的材料移动机制一样的 microconstituents 的特定的特征被讨论。合金的观察行为也通过他们的影响表面和表面下的区域的特征进一步被证实。

Effect of magnesium on the aluminothermic reduction rate of zinc oxide obtained from spent alkaline battery anodes for the preparation of Al–Zn–Mg alloys

The aluminothermic reduction of zinc oxide（ZnO） from alkaline battery anodes using molten Al may be a good option for the elaboration of secondary 7000-series alloys. This process is affected by the initial content of Mg within molten Al, which decreases the surface tension of the molten metal and conversely increases the wettability of ZnO particles. The effect of initial Mg concentration on the aluminothermic reduction rate of ZnO was analyzed at the following values： 0.90wt%, 1.20wt%, 4.00t%, 4.25wt%, and 4.40wt%. The ZnO particles were incorporated by mechanical agitation using a graphite paddle inside a bath of molten Al maintained at a constant temperature of 1123 K and at a constant agitation speed of 250 r/min, the treatment time was 240 min and the ZnO particle size was 450？500 mesh. The results show an increase in Zn concentration in the prepared alloys up to 5.43wt% for the highest initial concentration of Mg. The reaction products obtained were characterized by scanning electron microscopy and X-ray diffraction, and the efficiency of the reaction was measured on the basis of the different concentrations of Mg studied.

STUDIES OF LOW-CONCENTRATION CHROMATE PASSIVE FILM FOR ZINC-BASED ALLOY COATED STEEL WIRES

The corrosion resistance of a low concentration chromate passive film for zinc based alloy coated steel wires was assessed by salt spray and electrochemical corrosion tests. XPS and AES analyses showed that the composition of such chromate passive film was S 5 5, Na 3 4, C 11 8, Ti 7 9, O 41 6, Cr 13 7, Zn 16 0.