Design biodegradable Zn alloys: Second phases and their significant influences on alloy properties

Alloying combined with plastic deformation processing is widely used to improve mechanical properties of pure Zn.As-cast Zn and its alloys are brittle.Beside plastic deformation processing,no effective method has yet been found to eliminate the brittleness and even endow room temperature super-ductility.Second phase,induced by alloying,not only largely determines the ability of plastic deformation,but also influences strength,corrosion rate and cytotoxicity.Controlling second phase is important for designing biodegradable Zn alloys.In this review,knowledge related to second phases in biodegradable Zn alloys has been analyzed and summarized,including characteristics of binary phase diagrams,volume fraction of second phase in function of atomic percentage of an alloying element,and so on.Controversies about second phases in Zn-Li,Zn-Cu and Zn-Fe systems have been settled down,which benefits future studies.The effects of alloying elements and second phases on microstructure,strength,ductility,corrosion rate and cytotoxicity have been neatly summarized.Mg,Mn,Li,Cu and Ag are recommended as the major alloying elements,owing to their prominent beneficial effects on at least one of the above properties.In future,synergistic effects of these elements should be more thoroughly investigated.For other nutritional elements,such as Fe and Ca,refining second phase is a matter of vital concern.

Biodegradable Zn-0.5Li alloy rib plate:Processing procedure development and in vitro performance evaluation

Trauma kills more than four million people worldwide each year,with chest trauma accounting for 25%of these deaths.Rib fractures are the main manifestation of chest trauma.Biodegradable Zn alloys offer a new option to overcome clinical problems caused by permanent rib fracture internal fixation mate-rials,e.g.,long-term stress masking and secondary surgery.In this study,the fabrication procedure of biodegradable Zn-0.5Li alloy rib plates is successfully developed,which consists of casting,hot-warm rolling,cutting,and pressing sequentially.Biomechanical three-point bending performance of the Zn al-loy rib plates is comparable to that of commercial pure Ti rib plates,much higher than that of pure Zn rib plates.In addition,the Zn alloy exhibits the best antibacterial ability against E.coli and S.aureus among the three materials.Although the Zn alloy exhibits a weaker MC3T3 cytocompatibility than pure Ti,it is better than pure Zn.This study provides a foundation for the future development of various biodegrad-able Zn alloy rib plates.

Microstructure refinement in biodegradable Zn-Cu-Ca alloy for enhanced mechanical properties,degradation homogeneity,and strength retention in simulated physiological condition

Zn-1.0Cu-0.5Ca(TA15)alloy has shown promising characteristics of enhanced mechanical properties and biodegradability for absorbable cardiovascular stents,endovascular devices,and wound closure devices applications.In this study,the TA15 alloy for bioabsorbable biomedical applications is investigated.In the conventionally cast TA15(TA15-C)alloy,CaZn_(13) phase are present as a large dendritic network with an average size of 73.25±112.84μm,Hot rolling of the TA15-C alloy has broken the long and dendritic network of the CaZn_(13) phases,however,the refined phases are observed as segregations and the distribution is non-uniform.These segregated CaZn_(13) suffered heavy localised corrosion which lead to poor mechanical properties in the as-fabricated condition and after biodegradation.Ultrasonic treatment(UST)during casting is identified as an effective technique for the refinement and redistribution of CaZn_(13) particles in TA15 alloy,which successfully reduce the size of the CaZn_(13) phase to 10.91±4.65μm in the as-solidified condition.After hot rolling,the UST processed TA15(TA15-UST)shows improved mechanical properties due to grain refinement and the reduction in microstructural defects,i.e.the broken CaZn_(13) phase.Results of 8-week immersion corrosion tests showed that both alloys possess very similar corrosion rate.However,TA15-UST has markedly improved corrosion homogeneity compared to TA15-N which favours the retention of mechanical properties even after prolonged exposure to physiological fluids.

Microstructures, mechanical properties and in vitro corrosion behavior of biodegradable Zn alloys microalloyed with Al, Mn, Cu, Ag and Li elements

In this work,Zn microalloyed with Al,Mn,Cu,Ag and Li was cast,annealed and extruded.The results showed that addition of multiple trace elements causes significant change in the microstructures,mechanical properties and corrosion behavior of Zn-0.1Al-0.1Mn-0.1Cu-0.1Ag(^(1)ZM),Zn-0.1Al-0.1Mn-0.1Cu0.1Ag-0.1Li(^(2)ZM-0.1Li)and Zn-0.1Al-0.1Mn-0.1Cu-0.1Ag-0.35Li(^(3)ZM-0.35Li)alloys.Two ternary phases with the approximate compositions of Al_(13)Mn_(3)Zn_(34) and Al_(10)MnZn_(89) phases are formed in the casting and annealing processes of these alloys,respectively.Wavyβ-LiZn_(4) lamellae that have not been extensively reported are precipitated from the primary Zn dendrites in the casting process of ZM-0.35Li alloy.Also,Zn laths are precipitated from the eutecticβ-LiZn_(4) phase in the annealing process of ZM-0.35Li alloy.The above-mentioned phases are crushed or elongated in the as-extruded alloys,which play an important role in improving the strength of the alloys.All the as-extruded alloys have typical(0001)basal texture,accompanied with relatively low{0001}<1120>slip and high{1012}<1011>twinning Schmid factors,which are advantageous and disadvantageous to the strength enhancement of the alloys,respectively.All the as-cast alloys exhibit poor mechanical properties,especially low ductility.The as-extruded ZM alloy exhibits ultrahigh ductility,with an elongation of up to 82.2%±2.94%.The as-extruded ZM0.35Li alloy shows the best comprehensive mechanical properties,with yield strength,ultimate tensile strength,elongation and hardness of 380±1.6 MPa,449±7.4 MPa,62.3%±4.63%and 98±1.4 HV,respectively.Electrochemical corrosion rates of the ZM,ZM-0.1Li and ZM-0.35Li alloys are 0.241±0.004,0.206±0.006 and 0.189±0.008 mm/year,respectively.In vitro immersion corrosion rates(after 26 d in SBF solution)of them are 0.134±0.005,0.125±0.004 and 0.121±0.003 mm/year,respectively.The as-extruded ZM-0.35Li alloy exhibits the best corrosion resistance.

300 MPa grade highly ductile biodegradable Zn-2Cu-(0.2-0.8)Li alloys with novel ternary phases

Although a few high-strength biodegradable Zn alloys with yield strengths(YSs)over 300 MPa in rolled state have been developed,their elongations(ELs)are generally less than 30%.This study developed rolled Zn-2Cu-x Li(x=0.2 wt.%,0.5 wt.%,0.8 wt.%)alloys with YSs of 316-335 MPa and ELs of 44%-61%.Three-dimensional atom probe(3DAP)and time of flight secondary ion mass spectrometry(TOF-SIMS)were employed to characterize Li distribution.Three kinds of Zn-Cu-Li ternary phases are identified,which are blockyε′-(Cu_(0.5),Li_(0.5))Zn 4,blockyβ′-(Li_(0.9),Cu_(0.1))Zn 4,and small roundγparticles with high Li content in the annealed state.Other identified phases are Zn,β-LiZn 4,andε-CuZn 4 phases.With the increase of Li content in the alloys,ε′phase with 6.50 at.%Cu transforms intoβ′phase with 2.12 at.%Cu,i.e.,the average level in the alloys.Withinε′phase,there exist nano-scale Li clusters andεphase,resulting inε′/εstructure.Dense Zn laths precipitate fromβ′phase,resulting inβ′/Zn lamellar structure.The lamel-lar structure is the matrix of Zn-2Cu-0.8Li and leads to near-isotropic plasticity.Electrochemistry tests show that degradation rates fall in the range of 153-196μm/year,which decrease with Li content.All the alloys exert positive effects on the growth of MC3T3-E1 cells with 10%extract.This research reveals how microstructure evolves in Zn-2Cu-x Li alloys,which lays the foundation for their future applications.

300 MPa grade biodegradable high-strength ductile low-alloy(BHSDLA)Zn-Mn-Mg alloys:An in vitro study

300 MPa grade biodegradable Zn-(0.6,0.8)Mn-(<0.1)Mg alloys with yield strengths>300 MPa and elongations>15%have been developed,which are designated as Zn06Mn006Mg(HE)and Zn08Mn005Mg(HE)in as-extruded state.They are the newest members of a small group of biodegradable Zn alloys with mechanical properties beyond the generally accepted benchmark for orthopedic implants.Immersed in simulated body fluid for 30 days,Zn06Mn006Mg(HE)and Zn08Mn005Mg(HE)exhibit corrosion rates of 38 and 53μm y^(-1),respectively.They show high antibacterial rates of 93%-97%against E.coli.In 25%-75%extracts of both the alloys,MC3T3-E1 cell viabilities for 1 day and 3 days are all over 100%,indicating complete cytocompatibility.In 100%extracts for 3 days,both alloys show non-toxicity.After a longtime room temperature storage of 72 weeks,natural embrittling alike Zn-Mg alloys does not happen.The Zn-Mn-Mg alloys still have mechanical properties exceeding the benchmark by a large margin.The in vitro study shows the newly developed BHSDLA Zn-Mn-Mg alloys are promising candidates for orthopedic implants.

Structural and mechanical aspects of hypoeutectic Zn–Mg binary alloys for biodegradable vascular stent applications

The study is concerned with the mechanical properties of Zn and three Zn–Mg double alloys with Mg concentrations:0.5%,1.0%and 1.5%in the form of rods with a diameter of 5 mm as potential materials for use in biodegradable medical implants,such as vascular stents.The materials were cast,next conventionally hot extruded at 250°C and finally,hydrostatically extruded(HE)at ambient temperature.Occasionally HE process was carried at liquid nitrogen temperature or in combination with the ECAP process.After HE,the microstructure of the alloys was made up of fine-grainedαZn of mean grain size~1μm in a 2-phase coat of 50–200 nm nanograins of the fineαZn+Mg2Zn11 eutectic.The 3 to 4-fold reduction of grain size as a result of HE allowed an increase in yield strength from 100%to over 200%,elongation to fracture from 100%to thirty fold and hardness over 50%compared to the best literature results for similar alloys.Exceptions accounted for elongation to fracture in case of Zn-0.5 Mg alloy and hardness in case of Zn-1.5 Mg alloy,both of which fell by 20%.For the Zn-0.5 Mg and Zn–1Mg alloys,after immersion tests,no corrosive degradation of plasticity was observed.Achieving these properties was the result of generating large plastic deformations at ambient temperature due to the application of high pressure forming with the cumulative HE method.The results showed that Zn–Mg binary alloys after HE have mechanical and corrosive characteristics,qualifying them for applications in biodegradable implants,including vascular stents.

Highly plastic Zn-0.3Ca alloy for guided bone regeneration membrane:Breaking the trade-off between antibacterial ability and biocompatibility

A common problem for Zn alloys is the trade-off between antibacterial ability and biocompatibility.This paper proposes a strategy to solve this problem by increasing release ratio of Ca^(2+)ions,which is realized by significant refinement of CaZn13 particles through bottom circulating water-cooled casting(BCWC)and rolling.Compared with conventionally fabricated Zn-0.3Ca alloy,the BCWC-rolled alloy shows higher antibacterial abilities against E.coli and S.aureus,meanwhile much less toxicity to MC3T3-E1 cells.Additionally,plasticity,degradation uniformity,and ability to induce osteogenic differentiation in vitro of the alloy are improved.The elongation up to 49%,which is the highest among Zn alloys with Ca,and is achieved since the sizes of CaZn_(13) particles and Zn grains are small and close.As a result,the long-standing problem of low formability of Zn alloys containing Ca has also been solved due to the elimination of large CaZn_(13) particles.The BCWC-rolled alloy is a promising candidate of making GBR membrane.

In Vitro Evaluation of the Feasibility of Commercial Zn Alloys as Biodegradable Metals

In this work, three widely used commercial Zn alloys （ZA4-1, ZA4-3, ZA6-1 ） were purchased and pre- pared by hot extrusion at 200℃. The microstructure, mechanical properties, corrosion behaviors, biocompatibility and hemocompatibility of Zn alloys were studied with pure Zn as control, Commercial Zn alloys demonstrated increased strength and superb elongation compared with pure Zn. Accelerated corrosion rates and uniform corrosion morphologies were observed in terms of commercial Zn alloys due to galvanic effects between Zn matrix and α-Al phases. 100% extracts of ZA4-1 and ZA6-1 alloys showed mild cytotoxicity while 50% extracts of all samples displayed good biocompatibility. Retardant cell cycle and inhibited stress fibers expression were observed induced by high concentration of Zn^2＋ releasing during corrosion. The hemolysis ratios of Zn alloys were lower than 1% while the adhered platelets showed slightly activated morphologies. In general, commercial Zn alloys possess promising mechanical properties, appropriate corrosion rates, significantly improved biocompatibility and good hemocompatibility in comparison to pure Zn. It is feasible to develop biodegradable metals based on commercial Zn alloys.

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.

Influence of laser surface remelting on microstructure and degradation mechanism in simulated body fluid of Zn-0.5Zr alloy

In this study,the Zn-0.5 wt%Zr(Zn-Zr)alloy was treated by laser surface remelting(LSR),and then the microstructure and degradation mechanism of the remelting layer were investigated and compared with the original as-cast alloy.The results reveal that after LSR,the bulky Zn(22)Zr phase in the original Zn-Zr alloy is dissolved and the coarse equiaxed grains transform into fine dendrites with a secondary dendrite arm space of about 100 nm.During the degradation process in simulated body fluid(SBF),the corrosion products usually concentrate at some certain areas in the original alloy,while the corrosion products distribute uniformly and loosely in the LSR-treated surface.After removing the corrosion products,it was found that the former suffers obvious pitting corrosion and then localized corrosion.The proposed mechanism is that corrosion initiates at grain boundaries and develops into the depth at some locations,and then leads to localized corrosion.For the LSR-treated sample,corrosion initiates at some active sites and propagates in all directions,corrosion takes place in the whole surface with distinctly uniform thickness reduction,while the localized corrosion and peeling of bulky Zn(22)Zr particles were eliminated.The electrochemical results also suggest the uniform corrosion of LSR-treated sample and localized corrosion of original sample.Based on the results,a new approach to regulate the corrosion mode of the biodegradable Zn alloy is proposed.