医用可降解Zn-Fe系锌合金的研究进展及展望  

Research progress and prospects of biodegradable Zn-Fe alloys

作　　者：石章智 赵善鹏 高克玮[1] 薛喆 姚生莲[1] 陈颖芝[1] 张晋 王鲁宁[1,2] SHI Zhangzhi;ZHAO Shanpeng;GAO Kewei;XUE Zhe;YAO Shenglian;CHEN Yingzhi;ZHANG Jin;WANG Luning(School of Materials Science and Engineering,University of Science and Technology Beijing,Beijing 100083,China;Institute of Materials Intelligent Technology,Liaoning Academy of Materials,Shenyang 110004,China;Orthopedics Department,Beijing Luhe Hospital,Capital Medical University,Beijing 101149,China;Sports Medicine Department,Beijing Jishuitan Hospital,Capital Medical University,Beijing 100035,China)

机构地区：[1]北京科技大学材料科学与工程学院,北京100083 [2]辽宁材料实验室材料智能技术研究所,沈阳110004 [3]首都医科大学附属北京潞河医院骨中心,北京101149 [4]首都医科大学附属北京积水潭医院运动医学科,北京100035

出　　处：《工程科学学报》2025年第4期717-726,共10页Chinese Journal of Engineering

基　　金：国家重点研发计划资助项目(2023YFB3812903);北京市科技新星计划资助项目(20220484178);国家自然科学基金资助项目(52231010,52301301);北京市医药卫生科技促进中心“优促计划”项目(YC202301QX0009);北京市通州区科技创新人才资助项目(JCQN2024023);首都医科大学附属北京潞河医院医学科技创新转化专项(LHCXZH-202403)。

摘　　要：因为生物相容性好、降解速率合适、抗菌性强等优点,锌成为继镁和铁之后很有发展前景的医用可降解金属.纯锌的强度低,加入营养元素Fe有强化效果.本文从微观组织、力学性能、降解行为与生物相容性四个方面综述了Zn‒Fe系锌合金的研究进展.该类锌合金中的主要第二相是底心单斜结构的FeZn_(13)相,它形成Ⅰ型{110}<‒1,1,‒2.81>孪晶,在合金熔体凝固过程中以孪晶面{110}为择优生长界面.FeZn_(13)的硬度为208 HV,约为纯锌的4倍,压缩断裂应变为0.5%.少量Fe的加入便可以形成体积分数较高的FeZn_(13)相,Fe质量分数为2.6%时,FeZn_(13)相的体积分数达到50%.在Zn‒Fe合金中添加Mg、Si、Mn和RE(稀土元素)可以提高强度,其中Mn的加入形成(Fe,Mn)Zn_(13)/MnZn_(13)核/壳结构第二相.FeZn_(13)的电位比Zn高317 mV,促进Zn相降解,降解产物主要为Zn(OH)_(2)、ZnO、Zn_(3)(PO_(4))_(2)、ZnCl_(2)、ZnCO_(3)和Ca_(3)(PO_(4))_(2).Zn‒Fe合金对多种细胞的存活率大于85%,溶血率小于5%,展现出较好的生物相容性.未来,Zn‒Fe系锌合金的发展要解决FeZn_(13)相粗大导致的强化效果和降解均匀性较低的关键问题,并在大动物体内开展该种材料制成的植入器械的长期研究以推进临床应用.Zinc has become a promising biodegradable metal,following magnesium and iron,owing to its excellent biocompatibility,suitable degradation rate,and strong antibacterial properties.However,the strength of pure Zn is relatively low,and the addition of the nutrient element Fe enhances its mechanical performance.This paper reviews the progress of Zn-Fe-based alloys,focusing on four aspects:microstructure,mechanical properties,degradation behavior,and biocompatibility.The main second phase in Zn-Fe-based alloys is the FeZn_(13) phase,characterized by a bottom-centered monoclinic structure,which can form{110}<-1,1,-2.81>type Ⅰ twins,with an orientation difference of about 71°between the twin and parent crystals.During the solidification of Zn-Fe alloy melts,the{110}twining plane serves as the preferred growth interface,causing FeZn_(13) to feature regular shapes within the Zn matrix.FeZn_(13) exhibits a hardness of 208 HV,about 4 times that of pure Zn,but has an ultimate compressive strain of just 0.5%,indicating brittleness typical of intermetallics.Adding a small amount of Fe considerably increases the volume fraction of the FeZn_(13) phase,reaching 50%at 2.6%FeZn_(13) content.At present,the minimum size of the FeZn_(13) phase can be refined to about 2μm using techniques like bottom circulating water-cooled casting(BCWC)and rolling.The crushing effect of rolling on FeZn_(13) particles is insufficient.It is necessary to combine liquid forming(i.e.,BCWC)to refine their sizes to less than 3μm.Incorporating elements such as Mg,Si,Mn,or rare-earth elements into Zn-Fe alloys can improve strength.For instance,Mn addition leads to the formation of(Fe,Mn)Zn_(13)/MnZn_(13) core/shell structured second phases.At present,the Zn-Fe based alloy with the highest comprehensive mechanical properties is“BCWC+rolled”Zn-0.3Fe alloy,with a yield strength(YS)of 218 MPa,ultimate tensile strength(UTS)of 264 MPa,and elongation to failure(EL)of 24%.For biodegradable alloys intended for orthopedic implants,the mechanical properties mus

关 键 词：锌合金 微观组织 力学性能 降解行为 生物相容性 

分 类 号：TG146.1[一般工业技术—材料科学与工程]