Fabrication, mechanical properties and in vitro degradation behavior of newly developed ZnAg alloys for degradable implant applications.

Zn and Zn-based alloys have been recognized as highly promising biodegradable materials for orthopedic implants and cardiovascular stents, due to their proved biocompatibility and, more importantly, lower corrosion rates compared to Mg alloys. However, pure Zn has poor mechanical properties. In this study, Ag is used as a promising alloying element to improve the mechanical properties of the Zn matrix as well as its biocompatibility and antibacterial properties. Accordingly, we design three ZnAg alloys with Ag content ranging from 2.5 to 7.0wt% and investigate the influence of the Ag content on mechanical and corrosion behavior of the alloys. The alloys are developed by casting process and homogenized at 410°C for 6h and 12h, followed by hot extrusion at 250°C with extrusion ratio of 14:1. Degradation behavior is assessed by electrochemical and static immersion tests in Hank's modified solution. Microstructural analysis reveals that hot extrusion significantly reduces the grain size of the alloys. Zn-7.0%Ag alloy shows a reasonably equiaxed and considerably refined microstructure with mean grain size of 1.5µm. Tensile tests at room temperature suggest that increasing the Ag content steadily enhances the tensile strength, while it does not affect the tensile ductility significantly. Zn-7.0%Ag shows high yield strength and ultimate tensile strength of 236MPa and 287MPa, respectively, which is due to the grain refinement and high volume fraction of fine AgZn3 particles precipitating along the grain boundaries during the extrusion process. Among all these alloys, Zn-7.0%Ag displayed superplasticity over a wide range of strain rates (from 5×10-4s-1 to 1.0×10-2s-1) providing the possibility of exploiting forming processes at rapid rates and/or even at lower temperatures. In addition, extruded alloys exhibit slightly faster degradation rate than pure Zn. X-ray diffraction results show the presence of ZnO and Zn(OH)2 on the degraded surfaces. Moreover, scanning electron microscopy imaging reveals that micro-galvanic corrosion is more pronounced on the alloys with higher Ag content due to the higher volume fraction of AgZn3 particles.

Novel Zn-based alloys for biodegradable stent applications: Design, development and in vitro degradation.

The search for a degradable metal simultaneously showing mechanical properties equal or higher to that of stainless steel and uniform degradation is still an open challenge. Several magnesium-based alloys have been studied, but their degradation rate has proved to be too fast and rarely homogeneous. Fe-based alloys show appropriate mechanical properties but very low degradation rate. In the present work, four novel Zn-Mg and two Zn-Al binary alloys were investigated as potential biodegradable materials for stent applications. The alloys were developed by casting process and homogenized at 350°C for 48h followed by hot extrusion at 250°C. Tube extrusion was performed at 300°C to produce tubes with outer/inner diameter of 4/1.5mm as precursors for biodegradable stents. Corrosion tests were performed using Hanks׳ modified solution. Extruded alloys exhibited slightly superior corrosion resistance and slower degradation rate than those of their cast counterparts, but all had corrosion rates roughly half that of a standard purity Mg control. Hot extrusion of Zn-Mg alloys shifted the corrosion regime from localized pitting to more uniform erosion, mainly due to the refinement of second phase particles. Zn-0.5Mg is the most promising material for stent applications with a good combination of strength, ductility, strain hardening exponent and an appropriate rate of loss of mechanical integrity during degradation. An EBSD analysis in the vicinity of the laser cut Zn-0.5Mg tube found no grain coarsening or texture modification confirming that, after laser cutting, the grain size and texture orientation of the final stent remains unchanged. This work shows the potential for Zn alloys to be considered for stent applications.