扫描速度对激光粉末床熔融NiTi合金耐腐蚀性能的影响

doi:10.3901/JME.2025.09.101

摘要/Abstract

摘要： 激光粉末床熔融(Laser powder bed fusion，LPBF)技术所制备的NiTi合金以及高自由度的成型、形状记忆效应和超弹性等多功能性在生物医疗领域获得了广泛的关注，具有巨大的应用潜力。然而，目前的研究多针对于其多孔结构设计降低弹性模量以及过程参数控制改善力学性能与功能特性等方面，对于其表面抗腐蚀能力的关注较少。与此同时，模拟体液中的耐腐蚀性能对于其医疗应用起着至关重要的作用。因此，在本研究中，重点研究激光加工过程中扫描速度对于耐腐蚀性的影响规律，分别选取扫描速度100 mm/s、400 mm/s、700 mm/s、1 000 mm/s, 1 300 mm/s和1 600 mm/s的六组样品进行分析，通过XRD、OM、SEM、EDS以及DSC等手段对不同样品的微观组织结构、致密度以及相组成等方面进行了详细的分析。采用电化学测试手段与浸泡实验分别对样品的短期与长期耐腐蚀性进行评价。结果表明：扫描速度对于样品耐蚀性具有重要影响，其耐腐蚀性能的变化与样品中B19’马氏体相的体积分数、样品表面气孔以及未熔合孔等缺陷密切相关。其中700 mm/s扫描速度下的样品的耐腐蚀性最优，腐蚀电流密度为(2.6±0.6)×10⁻⁷A/cm²。并且长期浸泡实验结果证明了低扫描速度下产生的球形气孔以及高扫描速度下产生的未熔合孔等部位优先被腐蚀破坏。而表面缺陷较少的扫描速度700 mm/s与1 000 mm/s样品，700 mm/s样品表面腐蚀产物更少，更不易被腐蚀破坏。本研究中扫描速度对于耐腐蚀性的影响规律，对于开发抗腐蚀性生物医用LPBF-NiTi合金提供了一定的指导作用。

关键词: 激光粉末床熔融, NiTi合金, 扫描速度, 耐腐蚀性, 模拟体液

Abstract: NiTi alloys produced using laser powder bed fusion (LPBF) technology have garnered significant attention in the biomedical field due to their high degree of freedom forming, shape memory effect, and superelasticity, showing great potential for various applications. However, current research primarily focuses on designing porous structures to reduce elastic modulus, optimizing process parameters to enhance mechanical properties and functional characteristics, while neglecting surface corrosion resistance. Yet, corrosion resistance in simulated body fluids is crucial for medical applications. This study primarily investigates the impact of scanning speed on corrosion resistance during laser processing. Six groups of samples with varying scanning speeds (100 mm/s, 400 mm/s, 700 mm/s, 1 000 mm/s, 1 300 mm/s and 1 600 mm/s) are analysed. The microstructure, density, and phase composition of the samples are meticulously examined using XRD, OM, SEM, EDS and DSC. Furthermore, the short and long-term corrosion resistance of the samples is assessed through electrochemical testing and immersion testing. The study demonstrates that the scanning speed significantly impacts the corrosion resistance of the sample. The corrosion resistance is closely linked to factors such as the volume fraction of the B19' martensitic phase, pores on the sample surface, and unfused pores. Notably, the sample scanned at 700 mm/s exhibits the highest corrosion resistance, with a corrosion current density of (2.6±0.6)×10⁻⁷A/cm². Long-term immersion experiments reveal that spherical pores generated at low scanning speeds and unfused pores at high scanning speeds are more susceptible to corrosion. Conversely, samples scanned at 700 mm/s and 1 000 mm/s display fewer surface defects, with the surface corrosion products of the 700 mm/s samples showing greater resistance to corrosion damage. This research sheds light on the impact of scanning speed on corrosion resistance, offering valuable insights for the advancement of corrosion-resistant biomedical LPBF-NiTi alloy.

Key words: laser powder bed fusion, NiTi alloy, scanning speed, corrosion resistance, simulated body fluids

中图分类号:

TG174

于征磊, 高德龙, 徐泽洲, 郭云婷, 牛士超, 韩志武, 张志辉, 任露泉. 扫描速度对激光粉末床熔融NiTi合金耐腐蚀性能的影响[J]. 机械工程学报, 2025, 61(9): 101-111.

YU Zhenglei, GAO Denglong, XU Zezhou, GUO Yunting, NIU Shichao, HAN Zhiwu, ZHANG Zhihui, REN Luquan. Effect of Scanning Speed on Corrosion Resistance of NiTi Alloy Melted by Laser Powder Bed[J]. Journal of Mechanical Engineering, 2025, 61(9): 101-111.

参考文献

[1] YU H,QIU Y,YOUNG M. Influence of Ni4Ti3 precipitate on pseudoelasticity of austenitic NiTi shape memory alloys deformed at high strain rate[J]. Materials Science & Engineering:A,2021,804:140753.
[2] WANG F,HE L,ZENG X. Triaxial tension-induced damage behavior of nanocrystalline NiTi alloy and its dependence on grain size[J]. Journal of Materials Science & Technology,2021,77:90-99.
[3] 刘明,李军,张延晓,等. 生物医用NiTi形状记忆合金腐蚀研究进展[J].稀有金属材料与工程,2021,50(11):4166-4173. LIU Ming,LI Jun,ZHANG Yanxiao,et al. Research Progress on corrosion of biomedical NiTi shape memory alloys[J]. Rare Metal Materials and Engineering,2021,50(11):4166-4173.
[4] 王蕴贤,张小农,孙康. NiTi合金的生物医用性能及其在医学领域的应用[J]. 稀有金属,2006,30(3):386-389. WANG Yunxian,ZHANG Xiaonong,SUN Kang. Biomedical properties of NiTi alloy and its application in medical field[J]. Rare Metals,2006,30(3):386-389.
[5] CHEN Q,THOUAS G. Metallic implant biomaterials[J]. Materials Science and Engineering:R:Reports,2015,87:1-57.
[6] LU H,MA H,LUO X. Microstructure,shape memory properties,and in vitro biocompatibility of porous NiTi scaffolds fabricated via selective laser melting[J]. Journal of Materials Research and Technology,2021,15:6797-6812.
[7] LU H,MA H,CAI W. Stable tensile recovery strain induced by a Ni4Ti3 nanoprecipitate in a Ni50.4Ti49.6 shape memory alloy fabricated via selective laser melting[J]. Acta Materialia,2021,219:117261.
[8] XUE L,ATLI K,PICAK S. Controlling martensitic transformation characteristics in defect-free NiTi shape memory alloys fabricated using laser powder bed fusion and a process optimization framework[J]. Acta Materialia,2021,215:117017.
[9] CAO Y,ZHOU X,CONG D. Large tunable elastocaloric effect in additively manufactured Ni-Ti shape memory alloys[J]. Acta Materialia,2020,194:178-189.
[10] XIONG Z,LI H,YANG H. Micro laser powder bed fusion of NiTi alloys with superior mechanical property and shape recovery function[J]. Additive Manufacturing,2022,57:102960.
[11] XIONG Z,LI M,HAO S. 3D-printing damage-tolerant architected metallic materials with shape recoverability via special deformation design of constituent material[J]. ACS Applied Materials& Interfaces,2021,13(33):39915-39924.
[12] XIONG Z,LI Z,SUN Z. Selective laser melting of NiTi alloy with superior tensile property and shape memory effect[J]. Journal Of Materials Science & Technology,2019,35(10):2238-2242.
[13] WANG X,YU J,LIU J. Humbeeck,effect of process parameters on the phase transformation behavior and tensile properties of NiTi shape memory alloys fabricated by selective laser melting[J]. Additive Manufacturing,2020,36:101545.
[14] SAEDI S,TURABI A,ANDANI M. The influence of heat treatment on the thermomechanical response of Ni- rich NiTi alloys manufactured by selective laser melting[J]. Journal of Alloys And Compounds,2016,677:204-210.
[15] SAEDI S,MOGHADDAM N,AMERINATANZI A. On the effects of selective laser melting process parameters on microstructure and thermomechanical response of Ni-rich NiTi[J]. Acta Materialia,2018,144:552-560.
[16] MARATTUKALAM J,SINGH A,SINGH S. Microstructure and corrosion behavior of laser processed NiTi alloy[J]. Materials Science& Engineering C Materials for Biological Applications,2015,57:309-313.
[17] QIU P,GAO P,WANG S. Study on corrosion behavior of the selective laser melted NiTi alloy with superior tensile property and shape memory effect[J]. Corrosion Science,2020,175:108891.
[18] YU Z,XU Z,GUO Y. Analysis of microstructure,mechanical properties,wear characteristics and corrosion behavior of SLM-NiTi under different process parameters[J]. Journal of Manufacturing Processes,2022,75:637-650.
[19] XUE L,ATLI K,ZHANG C. Laser powder bed fusion of defect-free NiTi shape memory alloy parts with superior tensile superelasticity[J]. Acta Materialia,2022,229:117781.
[20] YUAN L,GU D,LIN K. Electrically actuated shape recovery of NiTi components processed by laser powder bed fusion after regulating the dimensional accuracy and phase transformation behavior[J]. Chinese Journal of Mechanical Engineering:Additive Manufacturing Frontiers,2022,1(4):100056.
[21] GAN J,DUAN L,LI F. Effect of laser energy density on the evolution of Ni4Ti3 precipitate and property of NiTi shape memory alloys prepared by selective laser melting[J]. Journal of Alloys and Compounds,2021,869:159338.
[22] GUO Y,LI G,XU Z. Corrosion Resistance and biocompatibility of calcium phosphate coatings with a micro-nanofibrous porous structure on biodegradable magnesium alloys[J]. ACS Appl Bio Mater,2022,5(4) 1528-1537.
[23] ZHANG Z,YANG Y,GUO Y. The corrosion resistance and biomineralization of the DCPD-PCL coating on the surface of the additively manufactured NiTi alloy[J]. Surface & Coatings Technology,2023,466:129653.
[24] LIU X,GU D,YUAN L. Effect of laser printing mode on surface topography,microstructure,and corrosion property of additive manufactured NiTi alloy[J]. Advanced Engineering Materials,2023,25(20):2300184.
[25] QIU P,GAO P,WANG S. Study on corrosion behavior of the selective laser melted NiTi alloy with superior tensile property and shape memory effect[J]. Corrosion Science,2020,175:108891.
[26] LIU R,LI D. The mechanism responsible for high wear resistance of Pseudo-elastic TiNi alloy a novel tribo-material[J]. Wear,1999,777-783.
[27] GUO Y,XU Z,LIU M. The corrosion resistance,biocompatibility and biomineralization of the dicalcium phosphate dihydrate coating on the surface of the additively manufactured NiTi alloy[J]. Journal of Materials Research and Technology,2022,17:622-635.
[28] GUO Y,XU Z,WANG Q. Corrosion resistance and biocompatibility of graphene oxide coating on the surface of the additively manufactured NiTi alloy[J]. Progress in Organic Coatings,2022,164:106722.
[29] LIU Z,WANG T,XU Y. Double-layer calcium phosphate sandwiched siloxane composite coating to enhance corrosion resistance and biocompatibility of magnesium alloys for bone tissue engineering[J]. Progress in Organic Coatings,2023,177:107417.
[30] ZHANG Z,YANG Y,ZHANG J. Antibacterial activity of additive manufactured NiTi alloy improved by zinc oxide-doped DCPD-PCL composite coating,ceramics international[J]. Ceramics International,2024,50(1):897-908.
[31] WANG T,XU Y,LIU Z. A chitosan/polylactic acid composite coating enhancing the corrosion resistance of the bio-degradable magnesium alloy[J]. Progress in Organic Coatings,2023,178:107469.
[32] ABEDINI M,GHASEMI H,NILI M. Tribological behavior of NiTi alloy in martensitic and austenitic states[J]. Materials & Design,2009,30(10):4493-4497.
[33] AGHABEYGZADEH H,SHARIFI E,TAVOOSI M. Corrosion behavior of amorphous-nanocrystalline Ni50Ti50 shape memory alloy,archives of metallurgy and materials[J]. Archives of Metallurgy and Materials,2021,66(1):267-272.
[34] SAUGO M,FLAMINI D,SAIDMAN S. Low-voltage polarization in AOT solution to enhance the corrosion resistance of nitinol[J]. Journal of Materials Engineering and Performance,2021,30(3):1816-1824.
[35] SPEIRS M,HOOREWEDER B,HUMBEECK J. Fatigue behaviour of NiTi shape memory alloy scaffolds produced by SLM,a unit cell design comparison[J]. Journal of the Mechanical Behavior of Biomedical Materials,2017,70:53-59.