酸洗预处理对Ti-6Al-4V合金微观形貌与耐腐蚀性能的影响

doi:10.12337/zgkqzzxzz.2025.02.009

中国口腔种植学杂志 ›› 2025, Vol. 30 ›› Issue (1): 47-53.DOI: 10.12337/zgkqzzxzz.2025.02.009

酸洗预处理对Ti-6Al-4V合金微观形貌与耐腐蚀性能的影响

赵雨佳^1,2, 刘奇奇^1,2, 邱林³, 郝俊江⁴, 宿瀚奇⁴, 韩泽奎^1,2, 王心彧¹, 宿玉成^1,4,5,6,7

¹佳木斯大学口腔医学院佳木斯大学口腔医学工程实验中心黑龙江省生物医学材料及临床应用重点实验室 154002;
²佳木斯大学 154007;
³北京大学口腔医学院·口腔医院中心实验室 100081;
⁴北京卡尔斯医疗器械有限公司 102600;
⁵北京瑞城口腔医院 100032;
⁶北京口腔种植培训中心 100032;
⁷中国医学科学院北京协和医院口腔种植中心 100032

收稿日期:2024-07-30 出版日期:2025-02-28 发布日期:2025-02-24
通讯作者: 宿玉成,Email：yuchengsu@163.com,电话：010-66212299
作者简介:赵雨佳,硕士研究生在读,研究方向：金属材料3D打印与表面处理、数字化口腔种植;宿玉成,主任医师、教授、博士研究生导师,研究方向：口腔种植外科和正颌外科相关研究

Effect of acid pickling pretreatment on the microstructure and corrosion resistance of Ti-6Al-4V alloy

Zhao Yujia^1,2, Liu Qiqi^1,2, Qiu Lin³, Hao Junjiang⁴, Su Hanqi⁴, Han Zekui^1,2, Wang Xinyu¹, Su Yucheng^1,4,5,6,7

¹Stomatology Collage of Jiamusi University, Experimental Center for Stomatological Engineering, Jiamusi University, Key Laboratory of Oral Biomedical Materials and Clinical Application, Heilongjiang Province, Jiamusi 154002, Heilongjiang, China;
²Jiamusi University, Jiamusi 154007, Heilongjiang, China;
³Central Laboratory, Peking University School and Hospital of Stomatology, Beijing 100080, China;
⁴Beijing CRS Medical Device Co., Ltd, Beijing 102600, China;
⁵Beijing Citident Hospital of Stomatology, Beijing 100032, China;
⁶Beijing Implant Training College (BITC), Beijing 100032, China;
⁷Dental Implant Center, Peking Union Medical College Hospital, Chinese Academy of Medical Sciences, Beijing 100032, China

Received:2024-07-30 Online:2025-02-28 Published:2025-02-24
Contact: Su Yucheng, Email: yuchengsu@163.com, Tel: 0086-10-66212299

摘要/Abstract

摘要： 目的评估不同酸洗液酸洗预处理后六铝四钒钛（Ti-6Al-4V）合金的微观形貌和耐腐蚀性能的变化,以确定适合作为植入性生物材料的钛合金的酸洗方法。方法采用接触角测量、扫描电子显微镜、X射线能谱仪、电化学测试等研究HF+H₂SO₄酸洗液、HF+HNO₃酸洗液、HF酸洗液对Ti-6Al-4V合金试样进行酸洗后的微观形貌、亲水性能及耐腐蚀性能等。结果 Ti-6Al-4V合金试样在3种酸洗液中表现为不同的酸洗速率：HF+H₂SO₄酸洗组为0.088 μm/s、HF+HNO₃酸洗组为0.064 μm/s、HF酸洗组为0.097 μm/s。3组试样均表现出特征性的α+β相微观形貌,HF+HNO₃酸洗组和HF酸洗组β相占比大于HF+H₂SO₄酸洗组,HF酸洗组出现了氢化物相,光学显微镜下HF+HNO₃酸洗组试样点蚀现象最少;在模拟体液中做耐腐蚀性能测试,自腐蚀电位结果为去离子水组>HF+HNO₃酸洗组>HF+H₂SO₄酸洗组>HF酸洗组。结论经HF+HNO₃酸洗的Ti-6Al-4V合金试样表面平滑,接触角为47.63°±2.40°、失重率为1.11%±0.08%,可均匀去除有机杂质及氧化膜,C/Ti与O/Ti值分别下降至0.047±0.001、0.040±0.008,且有较高耐腐蚀性能,自腐蚀电位为-0.676 V。可选用HF+HNO₃酸洗液以获得耐腐蚀性能较高且表面清洁、均匀的植入性生物Ti-6Al-4V合金。

关键词: 六铝四钒钛, 酸洗, 模拟体液, 耐腐蚀性, β相

Abstract: Objective To evaluate the changes in the microstructure and corrosion resistance of Ti-6Al-4V alloy after different acid pickling pretreatments and to determine the optimal pickling method for titanium alloys used as implantable biomaterials. Methods The microstructure, hydrophilic properties, and corrosion resistance of machined Ti-6Al-4V alloy samples pickled with HF+H₂SO₄, HF+HNO₃, and HF solutions were analyzed using contact angle measurements, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and electrochemical tests. Results 1. Pickling rates varied among the three solutions: HF+H₂SO₄ (0.088 μm/s), HF+HNO₃ (0.064 μm/s), and HF (0.097 μm/s). 2. All groups exhibited characteristic α+β phase microstructures, with a higher proportion of β phase observed in the HF+HNO₃ and HF groups compared to the HF+H₂SO₄ group. The HF group also displayed hydride phases. Optical microscopy revealed the least pitting corrosion in the HF+HNO₃ group. 3. Corrosion resistance testing in simulated body fluids showed the following order of self-corrosion potential: control group > HF+HNO₃ group > HF+H₂SO₄ group > HF group. Conclusion HF+HNO₃ pickling produced Ti-6Al-4V alloy samples with smooth surfaces, a contact angle of 47.63°±2.40°, a weight loss rate of 1.11%±0.08%, and uniform removal of organic impurities and oxide films. The C/Ti and O/Ti ratios were reduced to 0.047±0.001 and 0.040±0.008, respectively. This treatment achieved higher corrosion resistance, with a self-corrosion potential of -0.676V. HF+HNO₃ is recommended as the preferred pickling solution for producing implantable Ti-6Al-4V alloys with superior corrosion resistance and a clean, uniform surface.

Key words: Ti-6Al-4V, Acid pickling, Simulated body fluids, Corrosion resistance, β phase

赵雨佳,刘奇奇,邱林,等. 酸洗预处理对Ti-6Al-4V合金微观形貌与耐腐蚀性能的影响[J]. 中国口腔种植学杂志, 2025, 30(1): 47-53. DOI: 10.12337/zgkqzzxzz.2025.02.009

Zhao Yujia, Liu Qiqi, Qiu Lin, Hao Junjiang, Su Hanqi, Han Zekui, Wang Xinyu, Su Yucheng. Effect of acid pickling pretreatment on the microstructure and corrosion resistance of Ti-6Al-4V alloy[J].Chinese Journal of Oral Implantology, 2025, 30(1): 47-53.DOI: 10.12337/zgkqzzxzz.2025.02.009.

参考文献

[1] Makowiecki A, Hadzik J, Błaszczyszyn A, et al.An evaluation of superhydrophilic surfaces of dental implants - a systematic review and meta-analysis[J]. BMC Oral Health, 2019,19(1):79. DOI: 10.1186/s12903-019-0767-8.
[2] Silva R, Agrelli A, Andrade AN, et al.Titanium dental implants: an overview of applied nanobiotechnology to improve biocompatibility and prevent infections[J]. Materials (Basel), 2022,15(9):3150. DOI: 10.3390/ma15093150.
[3] Kirmanidou Y, Sidira M, Drosou ME, et al.New Ti-alloys and surface modifications to improve the mechanical properties and the biological response to orthopedic and dental implants: a review[J]. Biomed Res Int, 2016,2016:2908570. DOI: 10.1155/2016/2908570.
[4] Velasco-Ortega E, Jos A, Cameán AM, et al.In vitro evaluation of cytotoxicity and genotoxicity of a commercial titanium alloy for dental implantology[J]. Mutat Res, 2010,702(1):17-23. DOI: 10.1016/j.mrgentox.2010.06.013.
[5] Pramanik A, Basak AK, Prakash C, et al.Recast layer formation during wire electrical discharge machining of titanium (Ti-6Al-4V) alloy[J]. J Mater Eng Perform, 2021,12(30):8926-8935. DOI:10.1007/s11665-021-06116-1.
[6] Hasçalık A, Çaydaş U.Electrical discharge machining of titanium alloy (Ti-6Al-4V)[J]. Appl Surf Sci, 2007, 253(22):9007-9016. DOI:10.1016/j.apsusc.2007.05.031.
[7] Chen SL, Lin MH, Huang GX, et al.Research of the recast layer on implant surface modified by micro-current electrical discharge machining using deionized water mixed with titanium powder as dielectric solvent[J]. Appl Surf Sci, 2014,311:47-53. DOI: 10.1016/j.apsusc.2014.04.204.
[8] Izman S, Kadir MRA, Anwar M, et al. Effect of pickling process on adhesion strength of Ti oxide layer on titanium alloy substrate[J]. Adv Mater Res, 2010, 146-147:1621-1630. DOI: 10.4028/www.scientific.net/AMR.146-147.1621.
[9] Zhu X, Chen J, Scheideler L, et al.Effects of topography and composition of titanium surface oxides on osteoblast responses[J]. Biomaterials, 2004,25(18):4087-4103. DOI: 10.1016/j.biomaterials.2003.11.011.
[10] Vera ML, Avalos MC, Rosenberger MR, et al.Evaluation of the influence of texture and microstructure of titanium substrates on TiO₂ anodic coatings at 60 V[J]. Mater Charact, 2017,131:348-358. DOI:10.1016/j.matchar.2017.07.005.
[11] 徐照英, 张腾飞, 苏永要, 等. 钛合金表面阳极氧化着色及摩擦学特性研究[J].真空科学与技术学报,2020,40(8):734-740. DOI: 10.13922/j.cnki.cjovst.2020.08.07.
Xu ZY, Zhang TF, Su YY, et al.Tribological properties of TC4 Ti-alloy surfaces modified by anodizing coloring[J].Chin J Vac Sci Technol,2020,40(8):734-740. DOI: 10.13922/j.cnki.cjovst.2020.08.07.
[12] Takeuchi M, Abe Y, Yoshida Y, et al.Acid pretreatment of titanium implants[J]. Biomaterials, 2003,24(10):1821-1827. DOI: 10.1016/s0142-9612(02)00576-8.
[13] 刘帅. 纳秒脉冲激光除锈机理与工艺实验研究[D]. 广州:广东工业大学, 2018.
Liu S, Study on mechanism and process of nanosecond pulse laser derusting[D].Guangzhou:Guangdong University of Technology,2018.
[14] Yue L, Wang Z, Li L.Material morphological characteristics in laser ablation of alpha case from titanium alloy[J]. Appl Surf Sci, 2012,258(20):8065-8071. DOI: 10.1016/j.apsusc.2012.04.173.
[15] Huang L, Kinnell P, Shipway PH.Parametric effects on grit embedment and surface morphology in an innovative hybrid waterjet cleaning process for alpha case removal from titanium alloys[J]. Procedia CIRP, 2013,6:594-599. DOI: 10.1016/j.procir.2013.03.077.
[16] Huang L, Kinnell P, Shipway PH.Removal of heat-formed coating from a titanium alloy using high pressure waterjet: influence of machining parameters on surface texture and residual stress[J]. J Mater Process Tech, 2015,223:129-138. DOI: 10.1016/j.jmatprotec.2015.03.053.
[17] Ji R, Wang H, Wang B, et al.Removing loose oxide layer and producing dense α-phase layer simultaneously to improve corrosion resistance of Ti-6Al-4V titanium alloy by coupling electrical pulse and ultrasonic treatment[J]. Surf Coat Tech, 2020,384:125329. DOI: 10.1016/j.surfcoat.2019.125329.
[18] 郑锋, 程挺宇, 张巧云. 钛及钛合金的酸洗技术[J].稀有金属与硬质合金, 2009,37(3):26-28. DOI: 10.3969/j.issn.1004-0536.2009.03.008.
Zheng F, Cheng TY, Zhang QY.Pickling technology of titanium and titanium alloy[J]. Rare Metals Cemented Carbides,2009,37(3):26-28. DOI: 10.3969/j.issn.1004-0536.2009.03.008.
[19] 罗鑫, 王超, 张书权, 等. 无HF成分的钛合金酸洗工艺[J].现代机械,2023,(3):94-97.
Luo X, Wang C, Zhang SQ, et al.HF-free acid pickling process of titanium alloy[J]. Modern Mach,2023,(3):94-97.
[20] 杜娟, 刘青茂, 王付胜, 等. Ti-6AL-4V钛合金在氢氟酸-硝酸体系下的缓蚀行为及机理[J].材料导报, 2019,33(6): 1000-1005. DOI: 10.11896/cldb.201906016.
Du J, Liu QM, Wang FS, et al.Corrosion inhibiting behaviors and mechanism of Ti-6Al-4V in hydrofluoric-nitric pickling solutions[J]. Mater Rep,2019,33(6):1000-1005. DOI: 10.11896/cldb.201906016.
[21] Brett CMA, Muresan I. The influence of artificial body fluids on metallic corrosion[J]. Key Eng Mater, 2002,230-232:459-462. DOI: 10.4028/www.scientific.net/KEM.230-232.459.
[22] Okazaki Y, Gotoh E.Comparison of metal release from various metallic biomaterials in vitro[J]. Biomaterials, 2005,26(1):11-21. DOI: 10.1016/j.biomaterials.2004.02.005.
[23] Liu S, Shin YC.Additive manufacturing of Ti6Al4V alloy: a review[J]. Mater Design, 2019,164:107552. DOI: 10.1016/j.matdes.2018.107552.
[24] Karambakhsh A, Afshar A, Malekinejad P.Corrosion resistance and color properties of anodized Ti-6Al-4V[J]. J Mater Eng Perform, 2012,21:121-127. DOI: 10.1007/s11665-010-9791-1.
[25] Wang CM, Zhang LJ, Ma YJ, et al.Hydrogen-surface interaction from first-principles calculations and its implication to hydrogen embrittlement mechanisms of titanium[J]. Appl Surf Sci, 2023,621:156871. DOI:10.1016/j.apsusc.2023.156871.
[26] Li X, Wang L,Fan L.Understanding the effect of fluoride on corrosion behavior of pure titanium in different acids[J]. Corros Sci, 2021, 192:109812. DOI: 10.1016/j.corsci.2021.109812.
[27] Melo-Fonseca F, Gasik M, Madeira S, et al.Surface characterization of titanium-based substrates for orthopaedic applications[J]. Mater Charact, 2021,177:111161. DOI: 10.1016/j.matchar.2021.111161.
[28] Elmer JW, Palmer TA, Babu SS, et al.In situ observations of lattice expansion and transformation rates of α and β phases in Ti-6Al-4V[J]. Materi Sci Eng, 2005,391(1-2):104-113. DOI: 10.1016/j.msea.2004.08.084.
[29] Vermesse E, Mabru C, Arurault L.Surface integrity after pickling and anodization of Ti-6Al-4V titanium alloy[J]. Appl Surf Sci, 2013,285:629-637. DOI: 10.1016/j.apsusc.2013.08.103.
[30] You L, Peng D, Zhou L, et al.Acid pickling process of titanium alloys and its investigation of intergranular corrosion and pitting corrosion[C]. Paris:Proceedings of the 2015 6th International Conference on Manufacturing Science and Engineering,2015. DOI: 10.2991/icmse-15.2015.300.
[31] 张新平, 于思荣, 何镇明, 等. 新型牙科用Ti合金人工体液中电化学腐蚀研究[J].腐蚀科学与防护技术, 2003, 15(5):249-253. DOI: 10.3969/j.issn.1002-6495.2003.05.001.
Zhang XP, Yu SR, He ZM, et al.Electrochemcal corrosion of new dental Ti alloys in an artificial body fluid[J]. Corros Sci Protect Technol,2003,15(5):249-253. DOI: 10.3969/j.issn.1002-6495.2003.05.001.
[32] Ong JL, Lucas LC, Raikar GN, et al.Electrochemical corrosion analyses and characterization of surface-modified titanium[J]. Appl Surf Sci, 1993,72(1):7-13. DOI: 10.1016/0169-4332(93)90036-B.
[33] Heakal F, Awad KA. Electrochemical corrosion and passivation behavior of titanium and its Ti-6Al-4V alloy in low and highly concentrated HBr solutions[J]. Int J Electrochem Sci, 2011,12,6:6483-6502.

酸洗预处理对Ti-6Al-4V合金微观形貌与耐腐蚀性能的影响

Effect of acid pickling pretreatment on the microstructure and corrosion resistance of Ti-6Al-4V alloy

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 1

编辑推荐

Metrics