Improvements in tribological and anticorrosion performance of porous Ti-6Al-4V via PEO coating

Abstract

Medical implants manufactured using biomaterial Ti-6Al-4V exhibit some disadvantages. Its higher elastic modulus than that of natural bone can cause stress shielding problems. This can be avoided using Ti-6Al-4V with pores in the implant structure. However, poor corrosion and tribocorrosion behaviors are yielded because of the large area exposed to the medium. To mitigate both issues, coating technologies can be applied. The plasma electrolytic oxidation (PEO) process is a cost-effective process that has been used successfully in nonporous Ti alloys. In this study, two PEO coatings with different amounts of Ca/P are used. However, reports regarding their application in porous materials are scarce. The effects of PEO treatments on corrosion and tribocorrosion in Ti-6Al-4V powder metallurgy are analyzed herein. The porous materials provide an efficient surface for PEO coatings, as demonstrated via scanning electron microscopy (SEM) and atomic force microscopy (AFM), and the porosity of the substrates improved the adherence of the coatings. The corrosion resistance measured via electrochemical impedance spectroscopy confirmed the beneficial effect of the coatings, particularly for long exposure time. The lower roughness, small pore size, and more compact film observed in the PEO-Ca/P sample resulted in favorable tribological and corrosion properties.

References

  1. [1]

    Geetha M, Singh A K, Asokamani R, Gogia A K. Ti based biomaterials, the ultimate choice for orthopaedic implants—A review. Prog Mater Sci 54(3): 397–425 (2009)

    Article  Google Scholar 

  2. [2]

    Martin F, García C, Blanco Y. Influence of residual porosity on the dry and lubricated sliding wear of a powder metallurgy austenitic stainless steel. Wear 328–329: 1–7 (2015)

    Article  Google Scholar 

  3. [3]

    Liu X, Chu P, Ding C. Surface modification of titanium, titanium alloys, and related materials for biomedical applications. Mater Sci Eng: R: Rep 47(3–4): 49–121 (2004)

    Article  Google Scholar 

  4. [4]

    Huiskes R, Weinans H, van Rietbergen B. The relationship between stress shielding and bone resorption around total hip stems and the effects of flexible materials. Clin Orthop Relat Res (274): 124–134 (1992)

  5. [5]

    Segal V M. Equal channel angular extrusion: From macromechanics to structure formation. Mater Sci Eng: A 271(1–2): 322–333 (1999)

    Article  Google Scholar 

  6. [6]

    Shbeh M M, Goodall R. Open celled porous titanium. Adv Eng Mater 19(11): 1600664 (2017)

    Article  Google Scholar 

  7. [7]

    Zhao Z W, Zhang G, Li H G. Preparation of calcium phosphate coating on pure titanium substrate by electro-deposition method. J Central South Univ Technol 11(2): 147–151 (2004)

    Article  Google Scholar 

  8. [8]

    Thull R, Grant D. Physical and chemical vapor deposition and plasma assisted techniques for coating titanium. In Titanium in Medicine. Brunette D M, Tengvall P, Textor M, Thomsen P, Eds. Berlin: Springer, 2001: 283–341.

    Chapter  Google Scholar 

  9. [9]

    Matykina E, Skeldon P, Thompson G E. Fundamental and practical evaluations of PEO coatings of titanium. Int Heat Treat Surf Eng 3(1–2): 45–51 (2009)

    Article  Google Scholar 

  10. [10]

    Ceschini L, Lanzoni E, Martini C, Prandstraller D, Sambogna G. Comparison of dry sliding friction and wear of Ti6Al4V alloy treated by plasma electrolytic oxidation and PVD coating. Wear 264(1–2): 86–95 (2008)

    Article  Google Scholar 

  11. [11]

    Zhang X L, Jiang Z H, Yao Z P, Wu Z D. Electrochemical study of growth behaviour of plasma electrolytic oxidation coating on Ti6Al4V: Effects of the additive. Corros Sci 52(10): 3465–3473 (2010)

    Article  Google Scholar 

  12. [12]

    Martini C, Ceschini L, Tarterini F, Paillard J M, Curran J A. PEO layers obtained from mixed aluminate-phosphate baths on Ti-6Al-4V: Dry sliding behaviour and influence of a PTFE topcoat. Wear 269(11–12): 747–756 (2010)

    Article  Google Scholar 

  13. [13]

    Jin Z M, Dowson D. Bio-friction. Friction 1(2): 100–113 (2013)

    Article  Google Scholar 

  14. [14]

    Matykina E, Berkani A, Skeldon P, Thompson G E. Realtime imaging of coating growth during plasma electrolytic oxidation of titanium. Electrochimica Acta 53(4): 1987–1994 (2007)

    Article  Google Scholar 

  15. [15]

    Chen F, Zhou H, Chen C, Xia Y J. Study on the tribological performance of ceramic coatings on titanium alloy surfaces obtained through microarc oxidation. Prog Org Coat 64(2–3): 264–267 (2009)

    Google Scholar 

  16. [16]

    Yerokhin A, Parfenov E V, Matthews A. In situ impedance spectroscopy of the plasma electrolytic oxidation process for deposition of Ca- and P-containing coatings on Ti. Surf Coat Technol 301: 54–62 (2016)

    Article  Google Scholar 

  17. [17]

    Shokouhfar M, Dehghanian C, Baradaran A. Preparation of ceramic coating on Ti substrate by plasma electrolytic oxidation in different electrolytes and evaluation of its corrosion resistance. Appl Surf Sci 257(7): 2617–2624 (2011)

    Article  Google Scholar 

  18. [18]

    Park M G, Choe H C. Corrosion behaviors of bioactive element coatings on PEO-treated Ti-6Al-4V alloys. Surf Coat Technol 376: 44–51 (2019)

    Article  Google Scholar 

  19. [19]

    Hussein R O, Nie X, Northwood D O. A spectroscopic and microstructural study of oxide coatings produced on a Ti-6Al-4V alloy by plasma electrolytic oxidation. Mater Chem Phys 134(1): 484–492 (2012)

    Article  Google Scholar 

  20. [20]

    Laurindo C A, Torres R D, Mali S A, Gilbert J L, Soares P. Incorporation of Ca and P on anodized titanium surface: Effect of high current density. Mater Sci Eng C Mater Biol Appl 37: 223–231 (2014)

    Article  Google Scholar 

  21. [21]

    Krupa D, Baszkiewicz J, Zdunek J, Smolik J, Słomka Z, Sobczak J W. Characterization of the surface layers formed on titanium by plasma electrolytic oxidation. Surf Coat Technol 205(6): 1743–1749 (2010)

    Article  Google Scholar 

  22. [22]

    Hwang I J, Choe H C, Brantley W A. Electrochemical characteristics of Ti-6Al-4V after plasma electrolytic oxidation in solutions containing Ca, P, and Zn ions. Surf Coat Technol 320: 458–466 (2017)

    Article  Google Scholar 

  23. [23]

    Reshadi F, Faraji G, Baniassadi M, Tajeddini M. Surface modification of severe plastically deformed ultrafine grained pure titanium by plasma electrolytic oxidation. Surf Coat Technol 316: 113–121 (2017)

    Article  Google Scholar 

  24. [24]

    Yao Z P, Jiang Y L, Jia F Z, Jiang Z H, Wang F P. Growth characteristics of plasma electrolytic oxidation ceramic coatings on Ti-6Al-4V alloy. Appl Surf Sci 254(13): 4084–4091 (2008)

    Article  Google Scholar 

  25. [25]

    Han I, Choi J H, Zhao B H, Baik H K, Lee I S. Micro-arc oxidation in various concentration of KOH and structural change by different cut off potential. Curr Appl Phys 7: e23–e27 (2007)

    Article  Google Scholar 

  26. [26]

    Philip J T, Mathew J, Kuriachen B. Tribology of Ti6Al4V: A review. Friction 7(6): 497–536 (2019)

    Article  Google Scholar 

  27. [27]

    Yu J M, Choe H C. Morphology changes and bone formation on PEO-treated Ti-6Al-4V alloy in electrolyte containing Ca, P, Sr, and Si ions. Appl Surf Sci 477: 121–130 (2019)

    Article  Google Scholar 

  28. [28]

    Shbeh M, Yerokhin A, Goodall R. Cyclic voltammetry study of PEO processing of porous Ti and resulting coatings. Appl Surf Sci 439: 801–814 (2018)

    Article  Google Scholar 

  29. [29]

    Menhal Shbeh M, Yerokhin A, Goodall R. Microporous titanium through metal injection moulding of coarse powder and surface modification by plasma oxidation. Appl Sci 7(1): 105 (2017)

    Article  Google Scholar 

  30. [30]

    Karaji Z G, Hedayati R, Pouran B, Apachitei I, Zadpoor A A. Effects of plasma electrolytic oxidation process on the mechanical properties of additively manufactured porous biomaterials. Mater Sci Eng: C 76: 406–416 (2017)

    Article  Google Scholar 

  31. [31]

    Toptan F, Alves A C, Pinto A M P, Ponthiaux P. Tribocorrosion behavior of bio-functionalized highly porous titanium. J Mech Behav Biomed Mater 69: 144–152 (2017)

    Article  Google Scholar 

  32. [32]

    Mabboux F, Ponsonnet L, Morrier JJ, Jaffrezic N, Barsotti O. Surface free energy and bacterial retention to saliva-coated dental implant materials: An in vitro study. Colloids Surf B Biointerfaces 39(4): 199–205 (2004)

    Article  Google Scholar 

  33. [33]

    Yerokhin A L, Nie X, Leyland A, Matthews A. Characterisation of oxide films produced by plasma electrolytic oxidation of a Ti-6Al-4V alloy. Surf Coat Technol 130(2–3): 195–206 (2000)

    Article  Google Scholar 

  34. [34]

    Alves S A, Bayón R, Igartua A, Saénz de Viteri V, Rocha L A. Tribocorrosion behaviour of anodic titanium oxide films produced by plasma electrolytic oxidation for dental implants. Lubr Sci 26(7–8): 500–513 (2014)

    Article  Google Scholar 

  35. [35]

    de Viteri V S, Bayón R, Igartua A, Barandika G, Moreno J E, Peremarch C P J, Pérez M M. Structure, tribocorrosion and biocide characterization of Ca, P and I containing TiO2 coatings developed by plasma electrolytic oxidation. Appl Surf Sci 367: 1–10 (2016)

    Article  Google Scholar 

  36. [36]

    US-ASTM. ASTM G99-05 Standard test method for wear testing with a pin-on-disk apparatus. ASTM, 2000.

  37. [37]

    Veiga C, Davim J P, Loureiro A J R. Properties and applications of titanium alloys: A brief review. Rev Adv Mater Sci 32: 14–24 (2012).

    Google Scholar 

  38. [38]

    Rautray T R, Narayanan R, Kim K H. Ion implantation of titanium based biomaterials. Prog Mater Sci 56(8): 1137–1177 (2011)

    Article  Google Scholar 

  39. [39]

    Yetim A F. Investigation of wear behavior of titanium oxide films, produced by anodic oxidation, on commercially pure titanium in vacuum conditions. Surf Coat Technol 205(6): 1757–1763 (2010)

    Article  Google Scholar 

  40. [40]

    Suzuki K, Aoki K, Ohya K. Effects of surface roughness of titanium implants on bone remodeling activity of femur in rabbits. Bone 21(6): 507–514 (1997)

    Article  Google Scholar 

  41. [41]

    de Viteri V S, Fuentes E. Titanium and titanium alloys as biomaterials. In Tribology-Fundamentals and Advancements. Rijeka #, Ed. Croatia: IntechOpen, 2013: 155–181.

    Google Scholar 

  42. [42]

    Zhou Y L, Niinomi M, Akahori T, Fukui H, Toda H. Corrosion resistance and biocompatibility of Ti-Ta alloys for biomedical applications. Mater Sci Eng: A 398(1–2): 28–36 (2005)

    Article  Google Scholar 

  43. [43]

    Myshkin N, Kovalev A. Adhesion and surface forces in polymer tribology—A review. Friction 6(2): 143–155 (2018)

    Article  Google Scholar 

  44. [44]

    Pałka K, Pokrowiecki R, Krzywicka M. Porous titanium materials and applications. Titanium for Consumer Applications. Amsterdam: Elsevier, 2019: 27–75.

    Google Scholar 

  45. [45]

    Sasikumar Y, Karuppusamy I, Naillayan R. Surface modification methods for titanium and its alloys and their corrosion behavior in biological environment: A review. J Bio- and Tribo-Corrosion 5(36): 5–36 (2019)

    Google Scholar 

  46. [46]

    Aziz-Kerrzo M, Conroy K G, Fenelon A M, Farrell S T, Breslin C B. Electrochemical studies on the stability and corrosion resistance of titanium-based implant materials. Biomaterials 22(12): 1531–1539 (2001)

    Article  Google Scholar 

  47. [47]

    Leitao E, Barbosa M A, De Groot K. In vitro testing of surface-modified biomaterials. J Mater Sci: Mater Med 9(9): 543–548 (1998)

    Google Scholar 

  48. [48]

    Pałka K, Pokrowiecki R, Krzywicka M. Porous Titanium Materials and Applications. In Titanium for Consumer Applications. Froes F, Ed. Amsterdam: Elsevier, 2019: 27–75.

    Chapter  Google Scholar 

  49. [49]

    Vieira A C, Ribeiro A R, Rocha L A, Celis J P. Influence of pH and corrosion inhibitors on the tribocorrosion of titanium in artificial saliva. Wear 261(9): 994–1001 (2006)

    Article  Google Scholar 

  50. [50]

    Manhabosco T M, Tamborim S M, dos Santos C B, Müller I L. Tribological, electrochemical and tribo-electrochemical characterization of bare and nitrided Ti6Al4V in simulated body fluid solution. Corros Sci 53(5): 1786–1793 (2011)

    Article  Google Scholar 

  51. [51]

    Khanmohammadi H, Allahkaram S R, Muñoz A I, Encinas E R, Rashidfarokhi A R. Tribocorrosion behavior of plasma electrolytic oxidation coatings on a Ti6Al4V substrate. In Proceedings of Eurocorr 2016, Montpellier, France, 2016: 1–5.

  52. [52]

    Meng Y G, Xu J, Jin Z M, Prakash B, Hu Y Z. A review of recent advances in tribology. Friction 8(2): 221–300 (2020)

    Article  Google Scholar 

  53. [53]

    Ríos J M, Quintero D, Castaño J G, Echeverría F, Gómez M A. Comparison among the lubricated and unlubricated tribological behavior of coatings obtained by PEO on the Ti6Al4V alloy in alkaline solutions. Tribol Int 128: 1–8 (2018)

    Article  Google Scholar 

  54. [54]

    Laurindo C A H, Lepienski C M, Amorim F L, Torres R D, Soares P. Mechanical and tribological properties of Ca/P-doped titanium dioxide layer produced by plasma electrolytic oxidation: Effects of applied voltage and heat treatment. Tribol Trans 61(4): 733–741 (2018)

    Article  Google Scholar 

  55. [55]

    Kikuchi M, Takahashi M, Okuno O. Elastic moduli of cast Ti-Au, Ti-Ag, and Ti-Cu alloys. Dent Mater 22(7): 641–646 (2006)

    Article  Google Scholar 

  56. [56]

    Niinomi M, Akahori T, Takeuchi T, Katsura S, Fukui H, Toda H. Mechanical properties and cyto-toxicity of new beta type titanium alloy with low melting points for dental applications. Mater Sci Eng: C 25(3): 417–425 (2005)

    Article  Google Scholar 

Download references

Acknowledgements

Financial support by Ministry of Education and Science (RTI2018-097990-B-I00) and the Junta de Castilla y Leon (VA275P18 and VA044G19) is gratefully acknowledged.

Author information

Affiliations

Authors

Corresponding author

Correspondence to C. Garcia-Cabezón.

Additional information

Cristina García Cabezón. She is a professor at the Engineers School of the University of Valladolid and and the co-head of the group UVASens, dedicated to the development of electrochemical sensors for the analysis of foods. She obtained a B.S.C. degree in Chemistry (U. Zaragoza, 1991) and obtained her Ph.D. degree in industrial engineering from the University of Valladolid (1998) where she is currently a professor at the Department of Materials Science.

For several years, her research was dedicated to the study of the electrochemical behavior of metals and metal nanoparticles and she became an expert in electrochemistry. Her investigation in the field of materials science and engineering is focused on corrosion, porous materials, and coatings. The materials in which these studies have been carried out are stainless steels, cobalt alloys, and titanium alloys.

In 2010, she joined the group UVASens, dedicated to the development of electrochemical sensors for the analysis of foods, where her skills in electrochemistry of metals and nanoparticles busted the research in the field of electronic tongues of the group. She has developed electrochemical sensors based on nanoparticles dedicated to the detection of antioxidants and the analysis in wines and milks. She is an author or co-author of 54 indexed articles (h-index 15). She has colaborations with several national and international groups. In particular, she is directing the collaboration with the group of Sensors of the I.P. Braganza (Portugal). She serves a referee of several journals related to electrochemistry (electrochimica acta, corrosion science, sensors, etc.). She reviews 12–15 papers per year. She regularly participates in contracts with industries.

Rights and permissions

Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made.

The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder.

To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Garcia-Cabezón, C., Rodríguez-Méndez, M.L., Borrás, V.A. et al. Improvements in tribological and anticorrosion performance of porous Ti-6Al-4V via PEO coating. Friction 9, 1303–1318 (2021). https://doi.org/10.1007/s40544-020-0480-2

Download citation

Keywords

  • Ti-based alloys
  • corrosion
  • tribocorrosion
  • surface modification