Department of Materials Science and Engineering, Michigan Technological University, Houghton, MI 49931, USA.
Department of Materials Science and Engineering, Michigan Technological University, Houghton, MI 49931, USA.
Acta Biomater. 2020 Mar 15;105:319-335. doi: 10.1016/j.actbio.2020.01.028. Epub 2020 Jan 23.
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 AgZn particles, distributing throughout the Zn matrix. Such precipitates triggered mechanical degradation through an activation of Zn/AgZn 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 AgZn 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 AgZn 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.
锌基合金因其生物相容性和优于镁的可降解性而被认为是有前途的心血管支架生物可吸收材料。然而,由于应变率敏感性和应变软化行为较强,导致强度较低且固有机械不稳定性,这使得锌合金的开发对于支架应用具有挑战性。在本研究中,我们开发了二元 Zn-4.0Ag 和三元 Zn-4.0Ag-xMn(其中 x=0.2-0.6wt%)合金。通过冷加工和随后对挤压合金进行热处理设计了一种实验方法,可以彻底研究晶粒尺寸和析出物的影响。微观结构观察表明,拉丝过程中发生了明显的晶粒细化,导致 Zn-4.0Ag 和 Zn-4.0Ag-0.6Mn 的超细晶(UFG)结构尺寸分别为 700nm 和 200nm。Mn 具有很强的晶粒细化作用,因为它促进了动态再结晶。此外,冷加工导致 AgZn 颗粒的动态析出,分布在整个 Zn 基体中。这些析出物通过激活 Zn/AgZn 晶界滑动引发机械降解,使 Zn-4.0Ag 和 Zn-4.0Ag-0.6Mn 的拉伸强度分别降低了 74%和 57%。观察到的析出软化导致冷拉合金具有很强的应变率敏感性。短时间退火通过减少 AgZn 分数显著减轻了机械不稳定性。由于富 Mn 颗粒对晶界的钉扎作用,三元合金线相对于无 Mn 对应物显示出更好的微观结构稳定性。最终,热处理后观察到腐蚀状态从局部到更均匀的转变,主要归因于 AgZn 析出物的溶解。意义声明:由于其良好的生物降解性,锌已被认为是支架应用的潜在可生物降解材料。然而,锌强度差和固有机械不稳定性促使研究人员寻找具有改善机械性能的锌合金。尽管已经进行了广泛的研究以满足上述关注点,但尚未报道具有稳定机械性能的 Zn 基合金。在这项工作中,系统地评估了 Zn-Ag 基合金的机械性能和稳定性,作为微观结构特征的函数。我们发现,Zn 合金的微观结构设计可用作找到一种有效策略,不仅可以提高强度和抑制机械不稳定性,而且可以通过增强腐蚀均匀性来最小化任何损伤。