医用可降解Zn-3Cu-xMn合金的制备及性能研究

doi:10.12068/j.issn.1005-3026.2023.08.006

摘要/Abstract

摘要： 为了探究Zn合金作为生物可降解心血管支架材料的可行性，通过铸造加反向热挤压的方法制备了Zn-3Cu-xMn(x=0， 0.5%， 1.0%， 1.5%)合金，运用金相显微镜、X射线衍射仪、扫描电子显微镜、拉伸测试、电化学测试和SBF浸泡腐蚀实验，探究Mn元素含量变化对Zn合金组织与性能的影响.结果表明，Zn-3Cu-xMn合金组织由Zn基体、CuZn₅和MnZn₁₃组成，随合金中Mn含量的升高，抗拉强度升高，屈服强度和延伸率均呈现先增后减的变化趋势，腐蚀速率提高，合金的浸泡腐蚀速率由0.063mm/a增至0.113mm/a.加入Mn元素的合金满足心血管支架材料的机械性能，腐蚀速率高于心血管支架材料的要求，因此，Zn合金具有成为生物可降解心血管支架材料的潜力.

关键词: 可降解心血管支架材料；Zn-3Cu-xMn合金；显微组织；机械性能；腐蚀速率.

Abstract: To investigate the feasibility of Zn alloy as biodegradable cardiovascular stent material， Zn-3Cu-xMn(x=0， 0.5%， 1.0%，1.5%)alloy was prepared by casting and reverse hot extrusion. The effects of Mn content on the microstructure and properties of the alloys were studied by optical metallographic microscope， XRD， SEM， tensile test， electrochemical test and SBF solution immersion corrosion. The results showed that the microstructure of Zn-3Cu-xMn alloy is composed of Zn matrix， CuZn₅ and MnZn₁₃. With the increase of Mn content in the alloy， the tensile strength increases， and the yield strength and elongation first increase and then decrease. Electrochemical tests and SBF solution immersion corrosion experiments indicated that the corrosion rate of Zn-3Cu-xMn alloy increases from 0.063mm/a to 0.113mm/a with the increase of Mn content in the alloy. The alloy with Mn element meets the mechanical properties of cardiovascular stent material， and the corrosion rate is higher than the requirements of cardiovascular stent material， so Zn alloy has the potential to become biodegradable cardiovascular stent material.

Key words: biodegradable cardiovascular stent material; Zn-3Cu-xMn alloy; microstructure; mechanical properties; corrosion rate

中图分类号:

TG146.2

张雅静，王金朋，陈鑫，吴航宇. 医用可降解Zn-3Cu-xMn合金的制备及性能研究[J]. 东北大学学报（自然科学版）, 2023, 44(8): 1104-1110.

ZHANG Ya-jing， WANG Jin-peng， CHEN Xin， WU Hang-yu. Preparation and Properties of Biodegradable Zn-3Cu-xMn Alloys[J]. Journal of Northeastern University(Natural Science), 2023, 44(8): 1104-1110.

参考文献

[1]Gao F，Hu Y，Li G，et al.Layer-by-layer deposition of bioactive layers on magnesium alloy stent materials to improve corrosion resistance and biocompatibility［J］.Bioactive Materials，2020，5(3):611-623.
[2]Sotomi Y，Onuma Y，Collet C，et al.Bioresorbable scaffold:the emerging reality and future directions［J］.Circulation Research，2017，120(8):1341-1352.
[3]Mauri L，Hsieh W H，Massaro J M，et al.Stent thrombosis in randomized clinical trials of drug-eluting stents［J］.New England Journal of Medicine，2007，356(10):1020-1029.
[4]Joner M，Aloke F V，Farb A，et al.Pathology of drug-eluting stents in humans［J］.Journal of the American College of Cardiology，2006，48(1):193-202.
[5]Palmerini T，Biondi-Zoccai G，Riva D D，et al.Stent thrombosis with drug-eluting and bare-metal stents:evidence from a comprehensive network meta-analysis［J］.The Lancet，2012，379(9824):1393-1402.
[6]Sambola A，Rello P，Soriano T，et al.Safety and efficacy of drug eluting stents vs bare metal stents in patients with atrial fibrillation: a systematic review and meta-analysis［J］.Thrombosis Research，2020，195:128-135.
[7]Arunkumar G，Rameshbabu A M，Parameswaran P，et al.Microstructural，cytotoxicity and antibacterial properties of bio-degradable Zn-2Cu-Ti alloy［J］.Materials Today:Proceedings，2021，37:3554-3556.
[8]Lin J，Tong X，Wang K，et al.Biodegradable Zn-3Cu and Zn-3Cu-0.2Ti alloys with ultrahigh ductility and antibacterial ability for orthopedic applications［J］.Journal of Materials Science & Technology，2021，68:76-90.
[9]Bowen P K，Shearier E R，Zhao S，et al.Biodegradable metals for cardiovascular stents:from clinical concerns to recent Zn-alloys［J］.Advanced healthcare Materids，2016，5(10):1121-1140.
[10]Mostaed E，Sikora-Jasinska M，Drelich J W，et al.Zinc-based alloys for degradable vascular stent applications［J］.Acta Biomaterialia，2018，71:1-23.
[11]Milazzo G，Caroli S，Braun R D.Tables of standard electrode potentials［J］.Journal of the Electrochemical Society，1978，125(6):261-272.
[12]Kabir H，Munir K，Wen C，et al.Recent research and progress of biodegradable zinc alloys and composites for biomedical applications:biomechanical and biocorrosion perspectives［J］.Bioactive Materials，2021，6(3):836-879.
[13]Tang Z，Niu J，Huang H，et al.Potential biodegradable Zn-Cu binary alloys developed for cardiovascular implant applications［J］.Journal of the Mechanical Behavior of Biomedical Materials，2017，72:182-191.
[14]Zhang W，Li P，Neumann B，et al.Chandler-loop surveyed blood compatibility and dynamic blood triggered degradation behavior of Zn-4Cu alloy and Zn［J］.Materials Science and Engineering C，2021，119:111594.
[15]Jia B，Yang H，Han Y，et al.In vitro and in vivo studies of Zn-Mn biodegradable metals designed for orthopedic applications［J］.Acta Biomaterialia，2020，108:358-372.
[16]Chen C，Yue R，Zhang J，et al.Biodegradable Zn-1.5Cu-1.5Ag alloy with anti-aging ability and strain hardening behavior for cardiovascular stents［J］.Materials Science and Engineering:C，2020，116:111172.
[17]Yue R，Huang H，Ke G，et al.Microstructure，mechanical properties and in vitro degradation behavior of novel Zn-Cu-Fe alloys［J］.Materials Characterization，2017，134:114-122.
[18]王利卿，孙世能，任玉平，等，Mg、Ca元素对可降解Zn合金组织性能影响［J］.东北大学学报(自然科学版)，2018，39(1):35-39.(Wang Li-qin，Sun Shi-neng，Ren Yu-ping，et al.Effect of Mg and Ca on microstructure and properties of degradable Zn alloy［J］.Journal of Northeatern University(Natural Sciene)，2018，39(1):35-39.)
[19]崔忠圻，覃耀春.金属学与热处理［M］.北京:机械工业出版社，2007.(Cui Zhong-qi，Qin Yao-chun.Metallography and heat treatment［M］.Beijing:China Machine Press，2007.)
[20]Yue R，Zhang J，Ke G，et al.Effects of extrusion temperature on microstructure，mechanical properties and in vitro degradation behavior of biodegradable Zn-3Cu-0.5Fe alloy［J］.Materials Science and Engineering:C，2019，105:110106.
[21]Shi Z Z，Gao X X，Zhang H J，et al.Design biodegradable Zn alloys:second phases and their significant influences on alloy properties［J］.Bioactive Materials，2020，5(2):210-218.
[22]Kubásek J，Vojtěch D，Jablonská E，et al.Structure，mechanical characteristics and in vitro degradation，cytotoxicity，genotoxicity and mutagenicity of novel biodegradable Zn-Mg alloys［J］.Materials Science and Engineering:C，2016，58:24-35.
[23]Huang S，Wu W，Su Y，et al.Insight into the corrosion behaviour and degradation mechanism of pure zinc in simulated body fluid［J］.Corrosion Science，2021，178:109-111.
[24]Jain D，Pareek S，Agarwala A，et al.Effect of exposure time on corrosion behavior of zinc-alloy in simulated body fluid solution:electrochemical and surface investigation［J］.Journal of Materials Research and Technology，2021，10:738-751.
[25]Liu X，Sun J，Qiu K，et al.Effects of alloying elements(Ca and Sr) on microstructure，mechanical property and in vitro corrosion behavior of biodegradable Zn-1.5Mg alloy［J］.Journal of Alloys and Compounds，2016，664:444-452.(上接第1077页)(Geng Rong，Wang Hong-yan，Liu Chang，et al.Computational offloading algorithm oriented to the space-earth integration network［J］.Journal of Northeastern University(Natural Science)，2022，43(3):376-382，413.)
[8]Zhao F，Chen Y，Zhang Y，et al.Dynamic offloading and resource scheduling for mobile edge computing with energy harvesting devices［J］.IEEE Transactions on Network and Service Management，2021，18(2):2154-2165.
[9]Li M，Cheng N，J Gao，et al.Energy-efficient UAV-assisted mobile edge computing:resource allocation and trajectory optimization［J］.IEEE Transactions on Vehicular Technology，2020，69(3):3424-3438.
[10]Yang B，Cao X，Li X，et al.Mobile-edge-computing-based hierarchical machine learning tasks distribution for IIOT［J］.IEEE Internet of Things Journal，2019，7(3):2169-2180.
[11]Cheng Z P，Min M H，Liwang M H，et al.Multi-agent DDPG-based joint task partitioning and power control in fog computing networks［J］.IEEE Internet of Things Journal，2021，9(1):104-116.
[12]Jararweh Y，Doulat A，Darabseh A，et al.SDMEC:software defined system for mobile edge computing［C］// 2016 IEEE International Conference on Cloud Engineering Workshop(IC2EW).Berlin:IEEE，2016:88-93.
[13]Chen M，Hao Y.Task offloading for mobile edge computing in software defined ultra-dense network［J］.IEEE Journal on Selected Areas in Communications，2018，36(3):587-597.
[14]Bi S，Zhang Y.Computation rate maximization for wireless powered mobile-edge computing with binary computation offloading［J］.IEEE Transactions on Wireless Communications，2018，17(6):4177-4190.
[15]Zhang H，Liu H，Cheng J，et al.Downlink energy efficiency of power allocation and wireless backhaul bandwidth allocation in heterogeneous small cell networks［J］.IEEE Transactions on Communications，2018，66(4):1705-1716.