The effects of alloying with Cu and Mn and thermal treatments on the mechanical instability of Zn-0.05Mg alloy.

The detrimental effect of natural aging on mechanical properties of zinc alloys restricts their application as bioresorbable medical implants. In this study, aging of Zn-0.05Mg alloy and the effect of 0.5 Cu and 0.1 Mn (in weight percent) addition on the microstructure and tensile properties were studied. The alloys were cold rolled, aged and annealed; aiming to investigate the effects of precipitates and grain size on the mechanical properties and their stability. TEM analysis revealed that in ultrafine-grained binary Zn-0.05Mg alloy, the natural aging occurred due to the formation of nano-sized Mg2Zn11 precipitates. After 90 days of natural aging, the yield strength and ultimate tensile strength of Zn-0.05Mg alloy increased from 197±4 MPa and 227±5 MPa to 233±8 MPa and 305±7 MPa, respectively, while the elongation was drastically reduced from 34±3% to 3±1%. This natural aging was retarded by adding the third element at either 0.1Mn or 0.5Cu quantities, which interacted with Mg in Zn solid solution and impeded the formation of Mg2Zn11 precipitates. The addition of Cu and Mn elements increased alloy's strength, ductility, and its mechanical stability at a room temperature. The measured tensile strength and elongation were 274±5 MPa and 41±1% for Zn-0.1Mn-0.05Mg and 312±2 MPa and 44±2% for Zn-0.5Cu-0.05Mg, respectively. Annealing the alloys at elevated temperatures caused increase in both grain size and dissolution of secondary phases, and both affected alloy deformation mechanisms.

Precipitation induced room temperature superplasticity in Zn-Cu alloys.

In this study, the effect of grain size and precipitates on tensile properties of Zn-1.0Cu alloy were investigated. The alloy was cold rolled and annealed to manipulate the grain size and precipitation of CuZn4 particles at grain boundaries. Cold rolling resulted in an almost ultrafinegrained structure alongside precipitation of nano-sized CuZn4 particles. Strain induced precipitates triggered room temperature superplasticity through activation of Zn/CuZn4 boundary sliding, exhibiting maximum elongation of 470% at the strain rate of 1.0 × 10-4 s-1. Short-time annealing led to significantly reduced strain rate sensitivity due to the reduction of CuZn4 fraction, while the grain size remained nearly intact. This suggests that precipitates rather than grain size mainly influence the mechanical properties of Zn alloys.

Improved biocompatibility of Zn-Ag-based stent materials by microstructure refinement.

The metallurgical engineering of bioresorbable zinc (Zn)-based medical alloys would greatly benefit from clarification of the relationships between material properties and biological responses. Here we investigate the biocompatibility of three Zn-based silver (Ag)-containing alloys, ranging from binary to quinary alloy systems. Selected binary and quinary Zn-Ag-based alloys underwent solution treatment (ST) to increase the solubility of Ag-rich phases within the Zn bulk matrix, yielding two different microstructures (one without ST and a different one with ST) with the same elemental composition. This experimental design was intended to clarify the relationship between elemental profile/microstructure and biocompatibility for the Zn-Ag system. We found that the quinary alloy system (Zn-4Ag-0.8Cu-0.6Mn-0.15Zr) performed significantly better, in terms of histomorphometry, than any alloy system we have evaluated to date. Furthermore, when solution treated to increase strength and ductility and reduce the fraction of Ag-rich phases, the quinary alloy's biocompatibility further improved. In vitro corrosion testing and metallographic analysis of in vivo implants demonstrated a more uniform mode of corrosion for the solution treated alloy. We conclude that Zn-Ag alloys can be engineered through alloying to substantially reduce neointimal growth. The positive effect on neointimal growth can be further enhanced by dissolving the AgZn3 precipitates in the Zn matrix to improve the corrosion uniformity. These findings demonstrate that neointimal-forming cells can be regulated by elemental additions and microstructural changes in degradable Zn-based implant materials. STATEMENT OF SIGNIFICANCE: The metallurgical engineering of bioresorbable zinc (Zn)-based medical alloys would greatly benefit from clarification of the relationships between material properties and biological responses. Here, selected binary and quinary Zn-Ag-based alloys underwent solution treatment (ST) to increase the solubility of Ag-rich phases within the Zn bulk matrix, yielding two different microstructures (one without ST and a different one with ST) with the same elemental composition. We found that applying a thermal treatment restores mechanical strength and mitigates the strain rate sensitivity of Zn-Ag alloys by dissolving AgZn3 precipitates. Ag-rich nano-precipitates in Zn decrease biocompatibility, a phenomenon that can be counteracted by dissolving the AgZn3 precipitates in the bulk Zn matrix.

Towards revealing key factors in mechanical instability of bioabsorbable Zn-based alloys for intended vascular stenting.

Zn-based alloys are recognized as promising bioabsorbable materials for cardiovascular stents, due to their biocompatibility and favorable degradability as compared to Mg. However, both low strength and intrinsic mechanical instability arising from a strong strain rate sensitivity and strain softening behavior make development of Zn alloys challenging for stent applications. In this study, we developed binary Zn-4.0Ag and ternary Zn-4.0Ag-xMn (where x = 0.2-0.6wt%) alloys. An experimental methodology was designed by cold working followed by a thermal treatment on extruded alloys, through which the effects of the grain size and precipitates could be thoroughly investigated. Microstructural observations revealed a significant grain refinement during wire drawing, leading to an ultrafine-grained (UFG) structure with a size of 700 nm and 200 nm for the Zn-4.0Ag and Zn-4.0Ag-0.6Mn, respectively. Mn showed a powerful grain refining effect, as it promoted the dynamic recrystallization. Furthermore, cold working resulted in dynamic precipitation of AgZn3 particles, distributing throughout the Zn matrix. Such precipitates triggered mechanical degradation through an activation of Zn/AgZn3 boundary sliding, reducing the tensile strength by 74% and 57% for Zn-4.0Ag and Zn-4.0Ag-0.6Mn, respectively. The observed precipitation softening caused a strong strain rate sensitivity in cold drawn alloys. Short-time annealing significantly mitigated the mechanical instability by reducing the AgZn3 fraction. The ternary alloy wire showed superior microstructural stability relative to its Mn-free counterpart due to the pinning effect of Mn-rich particles on the grain boundaries. Eventually, a shift of the corrosion regime from localized to more uniform was observed after the heat treatment, mainly due to the dissolution of AgZn3 precipitates. STATEMENT OF SIGNIFICANCE: Owing to its promising biodegradability, zinc has been recognized as a potential biodegradable material for stenting applications. However, Zn's poor strength alongside intrinsic mechanical instability have propelled researchers to search for Zn alloys with improved mechanical properties. Although extensive researches have been conducted to satisfy the mentioned concerns, no Zn-based alloys with stabilized mechanical properties have yet been reported. In this work, the mechanical properties and stability of the Zn-Ag-based alloys were systematically evaluated as a function of microstructural features. We found that the microstructure design in Zn alloys can be used to find an effective strategy to not only improve the strength and suppress the mechanical instability but also to minimize any damage by augmenting the corrosion uniformity.

Analysis of vascular inflammation against bioresorbable Zn-Ag based alloys.

Zinc (Zn) has emerged as a promising bioresorbable stent material due to its satisfactory corrosion behavior and excellent biocompatibility. However, for load bearing implant applications, alloying is required to boost its mechanical properties as pure Zn exhibits poor strength. Unfortunately, an increase in inflammation relative to pure Zn is a commonly observed side-effect of Zn alloys. Consequently, the development of a Zn-based alloy that can simultaneously feature improved mechanical properties and suppress inflammatory responses is a big challenge. Here, a bioresorbable, biocompatible Zn-Ag-based quinary alloy was comprehensively evaluated in vivo, in comparison to reference materials. The inflammatory and smooth muscle cellular response was characterized and correlated to metrics of neointimal growth. We found that implantation of the quinary alloy was associated with significantly improved inflammatory activities relative to the reference materials. Additionally, we found that inflammation, but not smooth muscle cell hyperplasia, significantly correlates to neointimal growth for Zn alloys. The results suggest that inflammation is the main driver of neointimal growth for Zn-based alloys and that the quinary Zn-Ag-Mn-Zr-Cu alloy may impart inflammation-resistance properties to arterial implants.

In Vitro Degradation of Absorbable Zinc Alloys in Artificial Urine.

Absorbable metals have potential for making in-demand rigid temporary stents for the treatment of urinary tract obstruction, where polymers have reached their limits. In this work, in vitro degradation behavior of absorbable zinc alloys in artificial urine was studied using electrochemical methods and advanced surface characterization techniques with a comparison to a magnesium alloy. The results showed that pure zinc and its alloys (Zn⁻0.5Mg, Zn⁻1Mg, Zn⁻0.5Al) exhibited slower corrosion than pure magnesium and an Mg⁻2Zn⁻1Mn alloy. The corrosion layer was composed mostly of hydroxide, carbonate, and phosphate, without calcium content for the zinc group. Among all tested metals, the Zn⁻0.5Al alloy exhibited a uniform corrosion layer with low affinity with the ions in artificial urine.

Zinc-based alloys for degradable vascular stent applications.

The search for biodegradable metals with mechanical properties equal or higher to those of currently used permanent biomaterials, such as stainless steels, cobalt chromium and titanium alloys, desirable in vivo degradation rate and uniform corrosion is still an open challenge. Magnesium (Mg), iron (Fe) and zinc (Zn)-based alloys have been proposed as biodegradable metals for medical applications. Over the last two decades, extensive research has been done on Mg and Fe. Fe-based alloys show appropriate mechanical properties, but their degradation rate is an order of magnitude below the benchmark value. In comparison, alongside the insufficient mechanical performance of most of its alloys, Mg degradation rate has proven to be too high in a physiological environment and corrosion is rarely uniform. During the last few years, Zn alloys have been explored by the biomedical community as potential materials for bioabsorbable vascular stents due to their tolerable corrosion rates and tunable mechanical properties. This review summarizes recent progress made in developing Zn alloys for vascular stenting application. Novel Zn alloys are discussed regarding their microstructural characteristics, mechanical properties, corrosion behavior and in vivo performance. STATEMENT OF SIGNIFICANCE: Numerous studies on magnesium and iron materials have been reported to date, in an effort to formulate bioabsorbable stents with tailorable mechanical characteristics and corrosion behavior. Crucial concerns regarding poor ductility and remarkably rapid corrosion of magnesium, and very slow degradation of iron, seem to be still not desirably fulfilled. Zinc was introduced as a potential implant material in 2013 due to its promising biodegradability and biocompatibility. Since then, extensive investigations have been made toward development of zinc alloys that meet clinical benchmarks for vascular scaffolding. This review critically surveys the zinc alloys developed since 2013 from metallurgical and biodegradation points of view. Microstructural features, mechanical, corrosion and in vivo performances of these new alloys are thoroughly reviewed and evaluated.

Influence of ECAP process on mechanical and corrosion properties of pure Mg and ZK60 magnesium alloy for biodegradable stent applications.

Equal channel angular pressing (ECAP) was performed on ZK60 alloy and pure Mg in the temperature range 150-250 °C. A significant grain refinement was detected after ECAP, leading to an ultrafine grain size (UFG) and enhanced formability during extrusion process. Comparing to conventional coarse grained samples, fracture elongation of pure Mg and ZK60 alloy were significantly improved by 130% and 100%, respectively, while the tensile strength remained at high level. Extrusion was performed on ECAP processed billets to produce small tubes (with outer/inner diameter of 4/2.5 mm) as precursors for biodegradable stents. Studies on extruded tubes revealed that even after extrusion the microstructure and microhardness of the UFG ZK60 alloy were almost stable. Furthermore, pure Mg tubes showed an additional improvement in terms of grain refining and mechanical properties after extrusion. Electrochemical analyses and microstructural assessments after corrosion tests demonstrated two major influential factors in corrosion behavior of the investigated materials. The presence of Zn and Zr as alloying elements simultaneously increases the nobility by formation of a protective film and increase the local corrosion damage by amplifying the pitting development. ECAP treatment decreases the size of the second phase particles thus improving microstructure homogeneity, thereby decreasing the localized corrosion effects.

Microstructure, texture evolution, mechanical properties and corrosion behavior of ECAP processed ZK60 magnesium alloy for biodegradable applications.

Ultra-fine grained ZK60 Mg alloy was obtained by multi-pass equal-channel angular pressing at different temperatures of 250°C, 200°C and 150°C. Microstructural observations showed a significant grain refinement after ECAP, leading to an equiaxed and ultrafine grain (UFG) structure with average size of 600nm. The original extrusion fiber texture with planes oriented parallel to extrusion direction was gradually undermined during ECAP process and eventually it was substituted by a newly stronger texture component with considerably higher intensity, coinciding with ECAP shear plane. A combination of texture modification and grain refinement in UFG samples led to a marked reduction in mechanical asymmetric behavior compared to the as-received alloy, as well as adequate mechanical properties with about 100% improvement in elongation to failure while keeping relatively high tensile strength. Open circuit potential, potentiodynamic and weight loss measurements in a phosphate buffer solution electrolyte revealed an improved corrosion resistance of UFG alloy compared to the extruded one, stemming from a shift of corrosion regime from localized pitting in the as-received sample to a more uniform corrosion mode with reduced localized attack in ECAP processed alloy. Compression tests on immersed samples showed that the rate of loss of mechanical integrity in the UFG sample was lower than that in the as-received sample.