380 MPa-30% grade biodegradable Zn-Mn-Mg-Ca alloy: Bimodal grain structure, large work-hardening strain, and enhanced biocompatibility.

Strain softening is a common issue for high-strength biodegradable Zn alloys. We developed Zn-0.6Mn-0.05Mg-0.05Ca alloy with a bimodal grain structure by extrusion and caliber rolling, refer to as ZMMC063 (CRD). The alloy exhibits the best strength-ductility synergy among Zn-Mn based alloys, which shows a yield strength of 386 MPa, an ultimate tensile strength of 443 MPa, and an elongation rate of 31%. This is the first 380 MPa-30% grade Zn-Mn based alloy, surpassing the previous reported Zn alloy with 320 MPa-20% grade. Its work-hardening strain reaches as high as 11.6%, which is 4 times greater than that of other 300 MPa Zn-Mn based alloys. This is owing to hetero-deformation induced strengthening effect of the bimodal grain. Additionally, it demonstrates for the first time that micro-galvanic corrosion happens between coarse and fine Zn grains, thereby accelerating degradation of the alloy. This provides a feasible protocol for controlling degradation of Zn alloys. Compared with the extruded Zn-0.6Mn-0.05Mg-0.05Ca alloy, refer to as ZMMC063 (HE), the increased release of Mg and Ca ions in ZMMC063 (CRD) improves tolerance of MC3T3-E1 cells to Zn. Consequently, ZMMC063 (CRD) shows higher antibacterial abilities against E. coli and S. aureus, meanwhile much less toxicity to MC3T3-E1 cells. Synergistic effect of Zn, Mg and Ca ions promote expression of ALP, COl-1, OCN and Runx-2, so that ZMMC063 (CRD) exhibits better ability to induce osteogenic differentiation. This paper suggests that ZMMC063 (CRD) is a promising candidate for orthopedic implants. STATEMENT OF SIGNIFICANCE: Previously the highest yield strength-elongation level of Zn-Mn based alloys is 320 MPa-20% grade. At such a high strength, the alloys' work-hardening strain (Ewh) values are below 4%. To further improve comprehensive properties of Zn-Mn based alloys, 380 MPa-30% grade Zn-0.6Mn-0.05Mg-0.05Ca alloy with bimodal grain structure is developed by extrusion and caliber rolling. The alloy's Ewh reaches as high as 11.6%, due to the hetero-deformation induced effect of bimodal grain structure. Additionally, micro-galvanic corrosion happens between bimodal grains, which accelerates the alloy's degradation. In vitro studies show that the alloy exhibits enhanced antibacterial activity, good cytocompatibility, and promising osteogenic effect, indicating that it is a promising candidate for orthopedic implants.