Skip to main content
Log in

Application of coupled substrate aging and TiO2 nanotube crystallization heat treatments in cold-rolled Ti–Nb–Sn alloys

  • Original Paper
  • Published:
Journal of Materials Science Aims and scope Submit manuscript

Abstract

Among titanium alloys, the β-type is the most indicated for orthopedic implants due to the reduced elastic modulus compared with α + β alloys. To improve osseointegration, the growth of a self-ordered titania nanotube layer onto the surface of titanium alloy implant pieces is a strategy used to accelerate bone growth. In this paper, the effects of heat treatment for titania nanotube crystallization on Ti–Nb and Ti–Nb–Sn alloys on the phase transformation, the Vickers hardness, and the elastic modulus of the substrate were investigated. TiO2 layers were grown onto cold-rolled Ti alloy substrates by anodization, and crystallization to anatase was followed by glazing-angle high-temperature X-ray diffraction with a heating ramp of 288 K/min to 623 K, where the samples were held for up to 4 h. The dynamic of the α- and ω-phase formation/dissolution was followed by X-ray diffraction. Transmission electron microscopy was used to confirm the presence of the α- and ω-phases and their volumes and dimensions. As a result of the TiO2 crystallization heat treatment, a continuous increase in the hardness was observed for the Ti–35Nb and Ti–35Nb–2Sn alloys, which is attributed to dissolution of α″ and the formation of ω precipitates. The same feature was observed for the elastic modulus. In the Ti–35Nb–4Sn alloy, the reverse decomposition of martensite resulted in the β phase and later in α phase precipitation. The aging of this alloy resulted in a homogeneous distribution of a high volumetric fraction of fine and dispersed α phase, which resulted in a hardness increase from 220 to 270 HV. This coupled heat treatment resulted in high hardness, low elastic modulus, and a nanotube with an anatase crystal phase.

This is a preview of subscription content, log in via an institution to check access.

Access this article

We’re sorry, something doesn't seem to be working properly.

Please try refreshing the page. If that doesn't work, please contact support so we can address the problem.

Institutional subscriptions

Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7

Similar content being viewed by others

References

  1. Long M, Rack HJ (1998) Titanium alloys in total joint replacement—a materials science perspective. Biomaterials 19:1621–1639

    Article  Google Scholar 

  2. Steinemann SG (1996) Metal implants and surface reactions. Injury 27:16–22

    Article  Google Scholar 

  3. Gepreel MA-H, Niinomi M (2013) Biocompatibility of Ti-alloys for long-term implantion. J Mech Behav Biomed 20:407–415

    Article  Google Scholar 

  4. Okazaki Y, Rao S, Tateishi T, Ito Y (1998) Cytocompatibility of various metal and development of new titanium alloys for medical implants. Mater Sci Eng A 243:250–256

    Article  Google Scholar 

  5. Hao YL, Li SJ, Sun SY, Zheng CY, Yang R (2007) Elastic deformation behavior of Ti-24Nb-4Zr-7.9Sn for biomedical applications. Acta Biomater 3:277–286

    Article  Google Scholar 

  6. Lee CM, Ju CP, Lin JHC (2002) Structure-property relationship of cast Ti-Nb alloys. J Oral Rehabil 29:314–322

    Article  Google Scholar 

  7. Guo S, Chen B, Meng Q, Zhao R, Zhao X (2013) Peculiar aging response of near β Ti-25Nb-2Mo-4Sn alloy for biomedical applications. Prog Nat Sci 23:1–6

    Article  Google Scholar 

  8. Li SJ, Cui TC, Hao YL, Yang R (2008) Fatigue properties of a metastable β-type titanium alloy with reversible phase transformation. Acta Biomater 4:305–317

    Article  Google Scholar 

  9. Elmay W, Prima F, Gloriant T, Bolle B, Zhong Y, Patoora E, Laheute P (2013) Effects of thermomechanical process on the microstructure and mechanical properties of a fully martensitic titanium-based biomedical alloy. J Mech Behav Biomed 18:47–56

    Article  Google Scholar 

  10. Matsumoto H, Watanabe S, Hanada S (2007) Microstructures and mechanical properties of metastable β TiNbSn alloys cold rolled and heat treated. J Alloy Compd 439:146–155

    Article  Google Scholar 

  11. Hanada S, Matsumoto H, Watanabe S (2005) Mechanical compatibility of titanium implants in hard tissues. Int Congr Ser 1284:239–247

    Article  Google Scholar 

  12. Li SJ, Niinomi M, Akahori T, Kasuga T, Yang R, Hao YL (2004) Fatigue characteristics of bioactive glass-ceramic-coated Ti–29Nb–13Ta–4.6Zr for biomedical application. Biomaterials 25:3369–3378

    Article  Google Scholar 

  13. Tan AW, Pingguan-Murphy B, Ahmad R, Akbar SA (2012) Review of titania nanotubes: fabrication and cellular response. Ceram Int 38:4421–4435

    Article  Google Scholar 

  14. Uchida M, Kin H-M, Kokubo T, Fujibayashi S, Nakamura T (2003) Structural dependence of apatite formation on titania gels is a simulated body fluid. J Biomed Mater Res A 64:164–170

    Article  Google Scholar 

  15. Oh S, Jin S (2006) Titanium oxide nanotubes with controlled morphology for enhanced bone growth. Mater Sci Eng C 26:1301–1306

    Article  Google Scholar 

  16. Popat KC, Leoni L, Grimes CA, Desai TA (2007) Influence of engineered titania nanotubular surfaces on bone cells. Biomaterials 28:3188–3197

    Article  Google Scholar 

  17. Hori N, Iwasa F, Ueno T, Takeuchi K, Tsukimura N, Yamada M, Hattori M, Yamamoto A, Ogawa T (2010) Selective cell affinity of biomimetic micro-nano-hybrid structured TiO2 overcomes the biological dilemma of osteoblasts. Dent Mater 26:275–287

    Article  Google Scholar 

  18. Minagar S, Berndt CC, Wang J, Ivanova E, Wen C (2012) A review of the application of anodization for the fabrication of nanotubes on metal implant surfaces. Acta Biomater 8:2875–2888

    Article  Google Scholar 

  19. Crawford GA, Chawla N, Das K, Bose S, Bandyopadhyay A (2007) Microstructure and deformation behavior of biocompatible TiO2 nanotubes on titanium substrate. Acta Biomater 3:359–367

    Article  Google Scholar 

  20. Ferreira CP, Gonçalves MC, Caram R, Bertazzoli R, Rodrigues CA (2013) Effects of substrate microstructure on the formation of oriented oxide nanotube arrays on Ti and Ti alloys. Appl Surf Sci 285:226–234

    Article  Google Scholar 

  21. Saji VS, Choe H, Brantley WA (2009) Nanotubular oxide layer formation on Ti–13Nb–13Zr alloy as a function of applied potential. J Mater Sci 44:3975–3982. doi:10.1007/s10853-009-3542-4

    Article  Google Scholar 

  22. Verissimo NC, Cremasco A, Rodrigues CA, Bertazzoli R, Caram R (2014) In situ characterization of the effects of Nb and Sn on the anatase-rutile transition in TiO2 nanotubes using high-temperature x-ray diffraction. Appl Surf Sci 307:372–381

    Article  Google Scholar 

  23. Choe H-C, Kim W-G, Jeong Y-H (2010) Surface characteristics of HA coated Ti-30Ta-xZr and Ti-30Nb-xZr alloys after nanotube formation. Surf Coat Technol 205:S305–S311

    Article  Google Scholar 

  24. Zhou X, Nguyen NT, Ozkan S, Schmuki P (2014) Anodic TiO2 nanotube layers: why does self-organized growth occur—a mini review. Electrochem Commun 46:157–162

    Article  Google Scholar 

  25. Luo B, Yang H, Liu S, Fu W, Sun P, Yuan M, Zhang Y, Liu Z (2008) Fabrication and characterization of self-organized mixed oxide nanotube arrays by electrochemical anodization of Ti-6Al-4V alloy. Mater Lett 62:4512–4515

    Article  Google Scholar 

  26. Jang S-H, Choe H-C, Ko Y-M, Brantley WA (2009) Electrochemical characteristics of nanotubes formed on Ti-Nb alloys. Thin Solid Films 517:5038–5043

    Article  Google Scholar 

  27. Oh S, Jin S (2006) Titanium oxide nanotubes with controlled morphology for enhanced bone growth. Mat Sci Eng C 26:1301–1306

    Article  Google Scholar 

  28. Xiong J, Wang Y, Li Y, Hodgson PD (2012) Phase transformations and thermal structure stability of titania nanotube films with different morphologies. Thin Solid Films 526:116–119

    Article  Google Scholar 

  29. Devaraj A, Williams REA, Nag S, Srinivasan R, Fraser HL, Banerjee R (2009) Three-dimensional morphology and composition of omega precipitates in a binary titanium-molybdenum alloy. Scr Mater 61:701–704

    Article  Google Scholar 

  30. Nag S, Banerjee R, Srinivasan R, Hwang JY, Harper M, Fraser HL (2009) ω-Assisted nucleation and growth of α precipitates in the Ti-5Al-5Mo-5V-3Cr-0.5Fe β titanium alloy. Acta Mater 57:2136–2147

    Article  Google Scholar 

  31. Banerjee D, Williams JC (2013) Perspectives on titanium science and technology. Acta Mater 61:844–879

    Article  Google Scholar 

  32. Lopes ESN, Cremasco A, Afonso CRM, Caram R (2011) Effects of double aging heat treatment on the microstructure, Vickers hardness and elastic modulus of Ti–Nb alloys. Mater Charact 62:673–680

    Article  Google Scholar 

  33. Cremasco A, Lopes ESN, Cardoso FF, Contieri RJ, Ferreira I, Caram R (2013) Effects of the microstructural characteristics of a metastable β Ti alloy on its corrosion fatigue properties. Int J Fatigue 54:32–37

    Article  Google Scholar 

  34. Zheng Y, Williams REA, Fraser HL (2016) Characterization of a previously unidentified ordered orthorhombic metastable phase in Ti-5Al-5Mo-5V-3Cr. Scr Mater 113:202–205

    Article  Google Scholar 

Download references

Acknowledgements

The authors thank the Brazilian Research Agency FAPESP (Grant No. 2014/00159-2) for their financial support and Prof. Hamish L. Fraser for making the SEM/TEM facilities in the CEMAS/Ohio State University available.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to A. Cremasco.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Cremasco, A., Lopes, E.S.N., Bertazzoli, R. et al. Application of coupled substrate aging and TiO2 nanotube crystallization heat treatments in cold-rolled Ti–Nb–Sn alloys. J Mater Sci 51, 6389–6399 (2016). https://doi.org/10.1007/s10853-016-9935-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-016-9935-2

Keywords

Navigation