Introduction: Titanium alloys containing the β phase have much better corrosion resistance. Some alloying elements, such as Mo, stabilize this phase. Among the Ti alloys that contain this element, the Ti-10Mo alloy is of particular importance. If this alloy is produced using selective laser melting (SLM), it will be an approach that is user-friendly due to the nature of the process. Methods: Samples were printed by SLM process. The constituent phases were determined by XRD. The microstructure was evaluated using optical and scanning electron microscopes. Corrosion behavior was evaluated by cyclic potentiodynamic polarization and electrochemical impedance spectroscopy. Findings: In the XRD pattern of pure Ti powder and printed sample, α and α/α' phases are seen, respectively. However, Ti-10Mo powder mixture consists of α and Mo phases, the β phase is more dominant in printed sample because of the Mo penetration in the Ti matrix. As well as, in the microstructure of Ti10Mo the beta phase is seen as Mo-rich streaks, whereas in pure Ti it is found relatively negligible as epitaxially grown primary columnar β grains with acicular α' martensite phase. Mo addition to pure Ti reduces its passive current density and stabilize oxide film. However, Ti-10Mo alloy, with its various phases and galvanic couples, experiences rupture of the passive oxide film at higher potentials, leading to pitting corrosion. The impedance module value of Ti-10Mo is higher than that of pure Ti. Both samples have a double passive oxide film, with Ti-10Mo alloy exhibiting higher resistance than pure Ti.

Subject Areas : journal of New Materials

Arezoo Pourshoja ¹ , karim Avak ² , مازیار آزادبه ³ , Mohamadreza Etminanfar ⁴ , Mehdi Ojaghi ⁵

1 - MSc Student, Faculty of Materials Engineering, Sahand University of Technology, Tabriz, Iran
2 - MSc Student, Faculty of Materials Engineering, Sahand University of Technology, Tabriz, Iran
3 - Professor, Faculty of Materials Engineering, Sahand University of Technology, Tabriz, Iran
4 - MaterAssociate Professor, Faculty of Materials Engineering, Sahand University of Technology, Tabriz, Iran
5 - Associate Professor, Faculty of Materials Engineering, Sahand University of Technology, Tabriz, Iran

Received: 2024-05-04 Accepted : 2024-06-16 Published : 2023-05-13

Keywords: Ti-10Mo, Pure Ti, Selective laser melting, Corrosion, Beta phase,

Abstract :

Introduction: Titanium alloys containing the β phase have much better corrosion resistance. Some alloying elements, such as Mo, stabilize this phase. Among the Ti alloys that contain this element, the Ti-10Mo alloy is of particular importance. If this alloy is produced using selective laser melting (SLM), it will be an approach that is user-friendly due to the nature of the process.

 

Methods: Samples were printed by SLM process. The constituent phases were determined by XRD. The microstructure was evaluated using optical and scanning electron microscopes. Corrosion behavior was evaluated by cyclic potentiodynamic polarization and electrochemical impedance spectroscopy.

 

Findings: In the XRD pattern of pure Ti powder and printed sample, α and α/α' phases are seen, respectively. However, Ti-10Mo powder mixture consists of α and Mo phases, the β phase is more dominant in printed sample because of the Mo penetration in the Ti matrix. As well as, in the microstructure of Ti10Mo the beta phase is seen as Mo-rich streaks, whereas in pure Ti it is found relatively negligible as epitaxially grown primary columnar β grains with acicular α' martensite phase. Mo addition to pure Ti reduces its passive current density and stabilize oxide film. However, Ti-10Mo alloy, with its various phases and galvanic couples, experiences rupture of the passive oxide film at higher potentials, leading to pitting corrosion. The impedance module value of Ti-10Mo is higher than that of pure Ti. Both samples have a double passive oxide film, with Ti-10Mo alloy exhibiting higher resistance than pure Ti.

 

References:

1. Duan R, Li S, Cai B, Zhu W, Ren F, Attallah MM. A high strength and low modulus metastable β Ti-12Mo-6Zr-2Fe alloy fabricated by laser powder bed fusion in-situ alloying. Addit Manuf. 2021 Jan 1;37. https://doi.org/10.1016/j.addma.2020.101708.
2. Geetha M, Singh AK, Asokamani R, Gogia AK. Ti based biomaterials, the ultimate choice for orthopaedic implants - A review. Vol. 54, Progress in Materials Science. 2009. p. 397–425. https://doi.org/10.1016/j.pmatsci.2008.06.004.
3. Mccracken M. Dental Implant Materials: Commerciallv Pure Tita&um and Titanium Alloys. Vol. 8, J Prosthod. 1999.
4. Pede D, Li M, Virovac L, Poleske T, Balle F, Müller C, et al. Microstructure and corrosion resistance of novel β-type titanium alloys manufactured by selective laser melting. Journal of Materials Research and Technology. 2022 Jul 1;19:4598–612. https://doi.org/10.1016/J.JMRT.2022.07.021.
5. Katzarov I, Malinov S, Sha W. Finite element modeling of the morphology of β to α phase transformation in Ti-6Al-4V alloy. Metall Mater Trans A Phys Metall Mater Sci [Internet]. 2002 [cited 2024 Apr 19];33(4):1027–40. https://doi.org/10.1007/S11661-002-0204-4/METRICS.
6. Commercially Pure (CP) Titanium and Alpha Alloys. Titanium [Internet]. 2007 Aug 16 [cited 2024 Apr 19];175–201. https://doi.org/10.1007/978-3-540-73036-1_4.
7. Materials Properties Handbook: Titanium Alloys - Google Books [Internet]
8. Wysocki B, Maj P, Krawczyńska A, Rożniatowski K, Zdunek J, Kurzydłowski KJ, et al. Microstructure and mechanical properties investigation of CP titanium processed by selective laser melting (SLM). J Mater Process Technol. 2017 Mar 1;241:13–23. https://doi.org/10.1016/J.JMATPROTEC.2016.10.022.
9. Dai N, Zhang J, Chen Y, Zhang LC. Heat Treatment Degrading the Corrosion Resistance of Selective Laser Melted Ti-6Al-4V Alloy. J Electrochem Soc. 2017;164(7):C428–34. https://doi.org/10.1149/2.1481707JES/META.
10. Kang N, Yuan H, Coddet P, Ren Z, Bernage C, Liao H, et al. On the texture, phase and tensile properties of commercially pure Ti produced via selective laser melting assisted by static magnetic field. Materials Science and Engineering: C. 2017 Jan 1;70:405–7. https://doi.org/10.1016/J.MSEC.2016.09.011.
11. Atapour M, Pilchak AL, Frankel GS, Williams JC. Corrosion behavior of β titanium alloys for biomedical applications. Materials Science and Engineering: C. 2011 Jul 20;31(5):885–91. https://doi.org/10.1016/J.MSEC.2011.02.005.

12. Pan J, Xu Z, Ma S, Li Y, Wang F. Process and Microstructure Properties of Ti-10mo-Xcu Alloys Fabricated by L-Ded. [cited 2024 Apr 19]; https://doi.org/10.2139/SSRN.4486664.
13. Oliveira NTC, Guastaldi AC. Electrochemical stability and corrosion resistance of Ti–Mo alloys for biomedical applications. Acta Biomater. 2009 Jan 1;5(1):399–405. https://doi.org/10.1016/J.ACTBIO.2008.07.010.
14. Zhao H, Xie L, Xin C, Li N, Zhao B, Communications LLMT, et al. Effect of molybdenum content on corrosion resistance and corrosion behavior of Ti-Mo titanium alloy in hydrochloric acid‏. Elsevier‏ [Internet]. [cited 2024 Apr 19]; Available from: https://www.sciencedirect.com/science/article/pii/S2352492822018736
15. Xu W, Chen M, Lu X, Zhang D wei, Singh H preet, Jian-shu Y, et al. Effects of Mo content on corrosion and tribocorrosion behaviours of Ti-Mo orthopaedic alloys fabricated by powder metallurgy. Corros Sci. 2020 May 15;168:108557. https://doi.org/10.1016/J.CORSCI.2020.108557
16. Alves A, Santana F, Rosa L, … SCMS and, 2004‏ undefined. A study on corrosion resistance of the Ti–10Mo experimental alloy after different processing methods‏. Elsevier‏APR Alves, FA Santana, LAA Rosa, SA Cursino, EN Codaro‏Materials Science and Engineering: C, 2004‏•Elsevier‏ [Internet]. [cited 2024 Apr 19]; Available from: https://www.sciencedirect.com/science/article/pii/S0928493104000827
17. Valiev RZ, Semenova IP, Latysh V V, Rack H, Lowe C, Petruzelka J, et al. Nanostructured Titanium for Biomedical Applications. 2008 [cited 2024 Apr 19]; https://doi.org/10.1002/adem.200800026.
18. Karanjai M, Sundaresan R, … GRMS and, 2007‏ undefined. Development of titanium based biocomposite by powder metallurgy processing with in situ forming of Ca–P phases‏. Elsevier‏M Karanjai, R Sundaresan, GVN Rao, TRR Mohan, BP Kashyap‏Materials Science and Engineering: A, 2007‏•Elsevier‏ [Internet]. [cited 2024 Apr 19]; Available from: https://www.sciencedirect.com/science/article/pii/S0921509306024105
19. Ehtemam-Haghighi S, Prashanth K, Design HAM&, 2016‏ undefined. Evaluation of mechanical and wear properties of TixNb7Fe alloys designed for biomedical applications‏. Elsevier‏S Ehtemam-Haghighi, KG Prashanth, H Attar, AK Chaubey, GH Cao, LC Zhang‏Materials & Design, 2016‏•Elsevier‏ [Internet]. [cited 2024 Apr 19]; Available from: https://www.sciencedirect.com/science/article/pii/S0264127516312011
20. Duan R, Li S, Cai B, Tao Z, Zhu W, … FRCPB, et al. In situ alloying based laser powder bed fusion processing of β Ti–Mo alloy to fabricate functionally graded composites‏. Elsevier‏R Duan, S Li, B Cai, Z Tao, W Zhu, F Ren, MM Attallah‏Composites Part B: Engineering, 2021‏•Elsevier‏ [Internet]. [cited 2024 Apr 19]; Available from: https://www.sciencedirect.com/science/article/pii/S1359836821004431
21. Trevisan F, Calignano F, Aversa A, Marchese G, Lombardi M, Biamino S, et al. Additive manufacturing of titanium alloys in the biomedical field: processes, properties and applications. J Appl Biomater Funct Mater. 2018 Apr 1;16(2):57–67. https://doi.org/10.5301/JABFM.5000371.
22. Herzog D, Seyda V, Wycisk E, Emmelmann C. Additive manufacturing of metals. Acta Mater. 2016 Sep 15;117:371–92. https://doi.org/10.1016/J.ACTAMAT.2016.07.019.
23. Dzogbewu TC, Du Preez WB. In situ alloying of Ti10Mo fused tracks and layers via laser powder bed fusion. Manuf Rev (Les Ulis) [Internet]. 2022 [cited 2024 Apr 19]; 9:23. Available https://doi.org/10.1051/MFREVIEW/2022022.
24. Kong D, Dong C, Ni X, Zhang L, Yao J, … CMJ of M, et al. Mechanical properties and corrosion behavior of selective laser melted 316L stainless steel after different heat treatment processes‏. Elsevier‏D Kong, C Dong, X Ni, L Zhang, J Yao, C Man, X Cheng, K Xiao, X Li‏Journal of Materials Science & Technology, 2019‏•Elsevier‏ [Internet]. [cited 2024 Apr 19]; Available from: https://www.sciencedirect.com/science/article/pii/S1005030219300453
25. آواک ک, آزادبه م, اسلامی س, اجاقی م. بررسی ریزساختار و مورفولوژی سطح و مقطع آلیاژ Mo10-Ti تولید شده به روش ذوب لیزری انتخابی. فصلنامه علمی - پژوهشی مواد نوین [Internet]. 2023 Oct 23 [cited 2024 May 3];14(53):1–20. Available from: https://jnm.marvdasht.iau.ir/article_6258.html
https://doi.org/10.30495/JNM.2024.32954.2026.
26. Qian C, Xu H, Applications QZJ of L, 2020‏ undefined. The influence of process parameters on corrosion behavior of Ti6Al4V alloy processed by selective laser melting‏. pubs.aip.org‏ [Internet]. [cited 2024 Apr 19]; Available from: https://pubs.aip.org/lia/jla/article/32/3/032010/222831
27. John C. Lippold. Effect of Microstructure. Welding Metallurgy and Weldability [Internet]. 2015 [cited 2024 Apr 19];224–62. Available from: https://books.google.com/books/about/Welding_Metallurgy_and_Weldability.html?id=EldwBQAAQBAJ
28. Kou S. Library. MRS Bull [Internet]. 2003 Sep 31 [cited 2024 Apr 19];28(9):674–5. https://doi.org/10.1557/MRS2003.197.
29. Basak A, Das S. Epitaxy and Microstructure Evolution in Metal Additive Manufacturing. Annu Rev Mater Res [Internet]. 2016 Jul 1 [cited 2024 Apr 19];46(Volume 46, 2016):125–49. https://doi.org/10.1146/ANNUREV-MATSCI-070115-031728/CITE/REFWORKS.
30. Thijs L, Verhaeghe F, Craeghs T, Humbeeck J Van, Kruth JP. A study of the microstructural evolution during selective laser melting of Ti–6Al–4V. Acta Mater. 2010 May 1;58(9):3303–12. https://doi.org/10.1016/J.ACTAMAT.2010.02.004.
31. Gong H, Rafi K, Gu H, Starr T, Manufacturing BSA, 2014‏ undefined. Analysis of defect generation in Ti–6Al–4V parts made using powder bed fusion additive manufacturing processes‏. Elsevier‏H Gong, K Rafi, H Gu, T Starr, B Stucker‏Additive Manufacturing, 2014‏•Elsevier‏ [Internet]. [cited 2024 Apr 19]; Available from: https://www.sciencedirect.com/science/article/pii/S2214860414000074
32. Kang N, Li Y, Lin X, Feng E, Huang W. Microstructure and tensile properties of Ti-Mo alloys manufactured via using laser powder bed fusion. J Alloys Compd. 2019 Jan 15;771:877–84. https://doi.org/10.1016/J.JALLCOM.2018.09.008.
33. Fornell J, Pellicer E, Van Steenberge N, Gonzá lez S, Gebert A, Suriñ ach S, et al. Improved plasticity and corrosion behavior in Ti–Zr–Cu–Pd metallic glass with minor additions of Nb: An alloy composition intended for biomedical applications‏. Elsevier‏J Fornell, E Pellicer, N Van Steenberge, S González, A Gebert, S Suriñach, MD Baró, J Sort‏Materials Science and Engineering: A, 2013‏•Elsevier‏ [Internet]. 2012 [cited 2024 Apr 19]; https://doi.org/10.1016/j.msea.2012.08.058.
34. Vany P. Standard Potentials in Aqueous Solutions. J Phys Chem Ref Data. 1978;18:1–21.
35. Jirarungsatian C, Science APC, 2010‏ undefined. Pitting and uniform corrosion source recognition using acoustic emission parameters‏. Elsevier‏C Jirarungsatian, A Prateepasen‏Corrosion Science, 2010‏•Elsevier‏ [Internet]. [cited 2024 Apr 19]; Available from: https://www.sciencedirect.com/science/article/pii/S0010938X0900434X
36. Dai N, Wu J, Zhang LC, Yin L, Yang Y, Jiang Y, et al. Pitting and etching behaviors occurring in duplex stainless steel 2205 in the presence of alternating voltage interference. Constr Build Mater. 2019 Mar 30;202:877–90. https://doi.org/10.1016/J.CONBUILDMAT.2019.01.084.
37. Dai N, Wu J, Zhang LC, Sun Y, Liu Y, Yang Y, et al. Alternating voltage induced oscillation on electrochemical behavior and pitting corrosion in duplex stainless steel 2205. Materials and Corrosion [Internet]. 2019 Mar 1 [cited 2024 Apr 19];70(3):419–33. https://doi.org/10.1002/MACO.201810438.
38. Dai N, Wan Y, Liu Y, Sun Y, Zhang LC, Jiang Y, et al. Studies on pitting corrosion in austenitic stainless steel interfered by square-wave alternating voltage with different parameters using multi-potential steps method. Materials and Corrosion [Internet]. 2018 Dec 1 [cited 2024 Apr 19];69(12):1741–57. https://doi.org/10.1002/MACO.201810199.
39. Frankel GS. Pitting Corrosion of Metals: A Review of the Critical Factors. J Electrochem Soc. 1998 Jun 1;145(6):2186–98. https://doi.org/10.1149/1.1838615/META.
40. Zhang B, Wang J, Wu B, Guo X, … YWN, 2018‏ undefined. Unmasking chloride attack on the passive film of metals‏. nature.com‏B Zhang, J Wang, B Wu, XW Guo, YJ Wang, D Chen, YC Zhang, K Du, EE Oguzie, XL Ma‏Nature communications, 2018‏•nature.com‏ [Internet]. [cited 2024 Apr 19]; Available from: https://www.nature.com/articles/s41467-018-04942-x
41. McCafferty E. Societal Aspects of Corrosion. Introduction to Corrosion Science. 2010;1–11. https://doi.org/10.1007/978-1-4419-0455-3_1.
42. Lu H, Zhang L, Gebert A, compounds LSJ of alloys and, 2008‏ undefined. Pitting corrosion of Cu–Zr metallic glasses in hydrochloric acid solutions‏. Elsevier‏HB Lu, LC Zhang, A Gebert, L Schultz‏Journal of alloys and compounds, 2008‏•Elsevier‏ [Internet]. [cited 2024 Apr 22]; Available from: https://www.sciencedirect.com/science/article/pii/S0925838807016660
43. Seo DI, Lee JB. Corrosion Characteristics of Additive-Manufactured Ti-6Al-4V Using Microdroplet Cell and Critical Pitting Temperature Techniques. J Electrochem Soc. 2019;166(13):C428–33. https://doi.org/10.1149/2.0571913JES/META.
44. Xie F, He X, Cao S, Lu X, science XQC, 2013‏ undefined. Structural characterization and electrochemical behavior of a laser-sintered porous Ti–10Mo alloy‏. Elsevier‏FX Xie, XB He, SL Cao, X Lu, XH Qu‏Corrosion science, 2013‏•Elsevier‏ [Internet]. [cited 2024 Apr 19]; Available from: https://www.sciencedirect.com/science/article/pii/S0010938X12005240
45. Xie F, He X, Cao S, Mei M, Qu X. Influence of pore characteristics on microstructure, mechanical properties and corrosion resistance of selective laser sintered porous Ti–Mo alloys for biomedical applications. Electrochim Acta. 2013 Aug 30;105:121–9. https://doi.org/10.1016/J.ELECTACTA.2013.04.105.
46. Metikoš-Huković M, Kwokal A, Piljac J. The influence of niobium and vanadium on passivity of titanium-based implants in physiological solution. Biomaterials. 2003 Sep 1;24(21):3765–75. https://doi.org/10.1016/S0142-9612(03)00252-7.
47. Lavos-Valereto IC, Wolynec S, Ramires I, Guastaldi AC, Costa I. Electrochemical impedance spectroscopy characterization of passive film formed on implant Ti-6AI-7Nb alloy in Hank’s solution. J Mater Sci Mater Med [Internet]. 2004 Jan [cited 2024 Apr 30];15(1):55–9. https://doi.org/10.1023/B:JMSM.0000010097.86245.74/METRICS.
48. Tamilselvi S, Vedarajan R, Tamilselvi S, Raman V, Rajendran N. Corrosion behaviour of Ti–6Al–7Nb and Ti–6Al–4V ELI alloys in the simulated body fluid solution by electrochemical impedance spectroscopy‏. Elsevier‏S Tamilselvi, V Raman, N Rajendran‏Electrochimica Acta, 2006‏•Elsevier‏ [Internet]. 2006 [cited 2024 Apr 30]; https://doi.org/10.1016/j.electacta.2006.06.018.
49. Shukla A, Science RBC, 2006‏ undefined. Effect of surface treatment on electrochemical behavior of CP Ti, Ti–6Al–4V and Ti–13Nb–13Zr alloys in simulated human body fluid‏. Elsevier‏AK Shukla, R Balasubramaniam‏Corrosion Science, 2006‏•Elsevier‏ [Internet]. [cited 2024 Apr 22]; Available from: https://www.sciencedirect.com/science/article/pii/S0010938X05001708
50. Chen J, Li C, Zhou L, Ren Y, Li C, Liao X, et al. The anisotropic of corrosion and tribocorrosion behaviors of Ti15Mo alloy fabricated by selective laser melting. Mater Charact. 2022 Aug 1;190:112000. https://doi.org/10.1016/J.MATCHAR.2022.112000.
51. Xie FX, He XB, Cao SL, Lu X, Qu XH. Structural characterization and electrochemical behavior of a laser-sintered porous Ti–10Mo alloy. Corros Sci. 2013 Feb 1;67:217–24. https://doi.org/10.1016/J.CORSCI.2012.10.036.