Quaternary Ti–20Nb–10Zr–5Ta alloy during immersion in simulated physiological solutions: formation of layers, dissolution and biocompatibility

  • Ingrid Milošev
  • Julija Hmeljak
  • Gregor Žerjav
  • Andrej Cör
  • Jose Maria Calderon Moreno
  • Monica Popa


Samples of the quaternary Ti–20Nb–10Zr–5Ta alloy were immersed in Hanks’ simulated physiological solution and in minimum essential medium (MEM) for 25 days. Samples of Ti metal served as controls. During immersion, the concentration of ions dissolved in MEM was measured by inductively coupled plasma mass spectrometry, while at the end of the experiment the composition of the surface layers was analyzed by X-ray photoelectron spectroscopy, and their morphology by scanning electron microscopy equipped for chemical analysis. The surface layer formed during immersion was comprised primarily of TiO2 but contained oxides of alloying elements as well. The degree of oxidation differed for different metal cations; while titanium achieved the highest valency, tantalum remained as the metal or is oxidized to its sub-oxides. Calcium phosphate was formed in both solutions, while formation of organic-related species was observed only in MEM. Dissolution of titanium ions was similar for metal and alloy. Among alloying elements, zirconium dissolved in the largest quantity. The long-term effects of alloy implanted in the recipient’s body were investigated in MEM, using two types of human cells—an osteoblast-like cell line and immortalized pulmonary fibroblasts. The in vitro biocompatibility of the quaternary alloy was similar to that of titanium, since no detrimental effects on cell survival, induction of apoptosis, delay of growth, or change in alkaline phosphatase activity were observed on incubation in MEM.


Inductively Couple Plasma Mass Spectrometry Minimum Essential Medium Metal Extract Quaternary Alloy Unexposed Control 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



This work was performed within the European transnational MNT ERA-Net II project (acronym SURFUNCTI). Support of the EU (ERDF) and Romanian Government infrastructure POS-CCE O 2.2.1 Project INFRANANOCHEM—No. 19/2009 is also gratefully acknowledged, as is the financial support by the Ministry of Education, Science and Sport of the Republic of Slovenia. Human osteosarcoma (HOS), a human osteoblast-like cell line, was kindly donated by Prof. J. Marc, Faculty of Pharmacy, University of Ljubljana. The authors thank Dr. V.S. Šelih of the National Institute of Chemistry, Ljubljana, Slovenia, for the ICP-MS measurements and Dr. R. Milačič of the Jožef Stefan Institute for fruitful discussion.


  1. 1.
    Kuo PC-H, Chou H-H, Lin Y-H, Peng P-W, Ou K-L, Lee W-R. Effects of surface functionalization on the nanostructure and biomechanical properties of binary titanium–niobium alloys. J Electrochem Soc. 2012;159:E103–7.CrossRefGoogle Scholar
  2. 2.
    Habazaki H, Uozumi M, Konno H, Shimizu K, Nagata S, Asami K, Matsumoto K, Takayama K, Oda Y, Skeldon P, Thompson GE. Influences of structure and composition on growth of anodic oxide films of Ti–Zr alloys. Electrochim Acta. 2003;28:3257–66.CrossRefGoogle Scholar
  3. 3.
    Oliveira NTC, Ferreira EA, Duarte LT, Biaggio SR, Rocha-Filho RC, Bocchi N. Corrosion resistance of anodic oxides on the Ti–50Zr and Ti–13Nb–13Zr alloys. Electrochim Acta. 2006;51:2068–75.CrossRefGoogle Scholar
  4. 4.
    López MF, Gutiérrez A, Jiménez JA. In vitro corrosion behaviour of titanium alloys without vanadium. Electrochim Acta. 2002;47:1359–64.CrossRefGoogle Scholar
  5. 5.
    Khan MA, Williams RL, Williams DF. The corrosion behaviour of Ti–6Al–4V, Ti–6Al–7Nb and Ti–13Nb–13Zr in protein solutions. Biomaterials. 1999;20:631–7.CrossRefGoogle Scholar
  6. 6.
    Samuel S, Nag S, Nasrazadani S, Ukirde V, El Bouanani M, Mohandas A, Nguyen K, Banarjee R. Corrosion resistance and in vitro response of laser-deposited Ti–Nb–Zr–Ta alloys for orthopedic implant applications. J Biomed Mater Res. 2010;94A:1251–6.Google Scholar
  7. 7.
    Karthega M, Raman V, Rajendran N. Influence of potential on the electrochemical behaviour of β titanium alloys in Hank’s solution. Acta Biomater. 2007;3(207):1019–23.CrossRefGoogle Scholar
  8. 8.
    Milošev I, Kosec T, Strehblow H-H. XPS and EIS study of the passive film formed on orthopaedic Ti–6Al–7Nb alloy formed in Hank’s physiological solution. Electrochim Acta. 2008;53:3547–58.CrossRefGoogle Scholar
  9. 9.
    López MF, Gutiérrez A, Jiménez JA. Surface characterization of new non-toxic titanium alloys for use as biomaterials. Surface Sci. 2001;482–485:300–5.CrossRefGoogle Scholar
  10. 10.
    Tanaka Y, Nakai M, Akahori T, Niinomi M, Tsutsumi Y, Doi H, Hanawa T. Characterization of air-formed surface oxide film on Ti–29Nb–13Ta–4.6Zr alloy surface using XPS and AES. Corrosion Sci. 2008;50:2111–6.CrossRefGoogle Scholar
  11. 11.
    Vasilescu C, Drob SI, Neacsu EI, Mirza Rosca JC. Surface analysis and corrosion resistance of a new titanium base alloy in simulated body fluids. Corrosion Sci. 2012;65:431–40.CrossRefGoogle Scholar
  12. 12.
    Okazaki Y, Gotoh E. Implant applications of highly corrosion-resistant Ti–15Zr–4Nb–4Ta alloy. Mater Trans. 2002;43:2943–8.CrossRefGoogle Scholar
  13. 13.
    Matsuno H, Yokoyama A, Watari F, Uo M, Kawasaki T. Biocompatibility and osteogenesis of refractory metal implants, titanium, hafnium, niobium, tantalum and rhenium. Biomaterials. 2001;22:1253–62.CrossRefGoogle Scholar
  14. 14.
    Payer M, Lorenzoni M, Jakse N, Kirmeier R, Dohr G, Stopper M, Pertl C. Cell growth on different zirconia and titanium surface textures: a morpholgic in vitro study. J Dental Implant (in German). 2010;4:338–51.Google Scholar
  15. 15.
    Rosalbino F, Macciò D, Giannoni P, Quarto R, Saccone A. Study of the in vitro corrosion behavior and biocompatibility of Zr–2.5Nb and Zr–1.5Nb–1Ta (at%) crystalline alloys. J Mater Sci Mater Med. 2011;22:1293–302.CrossRefGoogle Scholar
  16. 16.
    IARC Monograph on the Evaluation of Carcinogenic Risks to Human, vol 74, Surgical Implants and Other Foreign Bodies (1999).Google Scholar
  17. 17.
    Health-based Reassessment of Administrative Occupational Exposure Limits. Zirconium and zirconium compounds. The Hague: Health Council of the Netherlands; 2002.Google Scholar
  18. 18.
    Kim SE, Jeong HW, Hyun YT, Lee YT, Jung CH, Kim SK, Song JS, Lee JH. Elastic modulus and in vitro biocompatibility of Ti–xNb and Ti–xTa alloys. Met Mater Int. 2007;13:145–9.CrossRefGoogle Scholar
  19. 19.
    Sista S, Wen C, Hodgson PD, Pande G. The influence of surface energy of titanium–zirconium alloy on osteoblast cell function in vitro. J Biomed Mater Res. 2011;97A:27–36.CrossRefGoogle Scholar
  20. 20.
    Prigent H, Pellen-Mussi P, Cathelineau G, Bonnaure-Mallet M. Evaluation of the biocompatibility of titanium–tantalum alloys versus titanium. J Biomed Mater Res. 1998;39:200–6.CrossRefGoogle Scholar
  21. 21.
    Milošev I, Žerjav G, Calderon Moreno JM, Popa M. Electrochemical properties, chemical composition and thickness of passive film formed on novel Ti–20Nb–10Zr–5Ta alloy. Electrochim Acta. 2013;99:176–89.CrossRefGoogle Scholar
  22. 22.
    Popa M, Vasilescu E, Drob P, Raducanu D, Calderon Moreno JM, Ivanescu S, Vasilescu C, Drob SI. Microstructure, mechanical, and anticorrosive properties of a new Ti–20Nb–10Zr–5Ta alloy based on nontoxic and nonallergenic elements. Met Mater Int. 2012;18:639–45.CrossRefGoogle Scholar
  23. 23.
    Milošev I, Kapun B, Šelih VS. The effect of fluoride ions on the corrosion behaviour of Ti metal, and Ti–6Al–7Nb and Ti–6Al–4V alloys in artificial saliva. Acta Chim Slov. 2013;60:543–55.Google Scholar
  24. 24.
    Milošev I, Petrović Ž, Metikoš-Huković M. Influence of preparation methods on the properties of self-assembled films of ocytadecylphosphonate on Nitinol: XPS and EIS studies. Mater Sci Eng C. 2012;32:2604–16.CrossRefGoogle Scholar
  25. 25.
    Sherwood PMA. Introduction to studies of phosphorus–oxygen compounds by XPS. Surface Sci Spectra. 2002;9:62–6.CrossRefGoogle Scholar
  26. 26.
    Costa MT, Lenza MA, Gosch CS, Costa I, Ribeiro-Dias F. In vitro evaluation of corrosion and cytotoxicity of orthodontic brackets. J Dent Res. 2007;86:441–5.CrossRefGoogle Scholar
  27. 27.
    Markelc B, Tevz G, Cemazar M, Kranjc S, Lavrencak J, Zegura B, Teissie J, Sersa G. Muscle gene electrotransfer is increased by the antioxidant tempol in mice. Gene Ther. 2012;19:312–20.CrossRefGoogle Scholar
  28. 28.
  29. 29.
    Wagner CD, Naumkin AV, Kraut-Vass A, Allison JW, Powell CJ, Rumble JR Jr. NIST X-ray Photoelectron Spectroscopy Database, NIST Standard Reference Database 20, Version 3.5, Data compiled and evaluated.
  30. 30.
    Han JC, Liu AP, Zhu JQ, Tan ML, Wu HP. Effect of phosphorus content on structural properties of phosphorus incorporated tetrahedral amorphous carbon films. Appl Phys A. 2007;88:341–5.CrossRefGoogle Scholar
  31. 31.
    Moulder JF, Stickle WF, Sobol PE, Bomben KD. In: Chastain J, King Jr RC, editors. Handbook of X-ray photoelectron spectroscopy. Eden Prairie: Physical Electronics; 1995.Google Scholar
  32. 32.
    Malék J, Hnilica F, Vesely J, Smola B, Bártaková S, Vanek J. The influence of chemical composition and thermo-mechanical treatment on Ti–Nb–Ta–Zr alloys. Mater Des. 2012;35:731–40.CrossRefGoogle Scholar
  33. 33.
    Hoppe HW, Schultze JW. Electrochemical and XPS measurements on thin oxide films on zirconium. J Electroanal Chem. 1987;217:159–85.CrossRefGoogle Scholar
  34. 34.
    Mamun A, Schennach R, Parga JR, Mollah MYA, Hossain MA, Cocke DL. Passive film breakdown during anodic oxidation of zirconium in pH 8 buffer containing chloride and sulfate. Electrochim Acta. 2001;46:3343–50.CrossRefGoogle Scholar
  35. 35.
    Azuma M, Nakato Y, Tsubomora H. Oxygen and chlorine evolution on niobium-, zirconium- and other metal-nitride amorphous thin film electrodes prepared by the reactive RF sputtering technique. J Electroanal Chem. 1988;255:179–98.CrossRefGoogle Scholar
  36. 36.
    Abdel Rahim MA, Abdel Rahman AA, Khalil MW. Anion incorporation and its effect on the dielectric constant and growth rate of zirconium oxides. J Appl Electrochem. 1996;26(8):1037–43.Google Scholar
  37. 37.
    Huang BX, Wang K, Church JS, Li Y-S. Characterization of oxides on niobium by raman and infrared spectroscopy. Electrochim Acta. 1999;44:2571–7.CrossRefGoogle Scholar
  38. 38.
    Metikoš-Huković M, Kwokal A, Piljac J. Zje influence of niobium and vanadium on passivity of titanium-based implants in physiological solution. Biomaterials. 2003;24:3765–75.CrossRefGoogle Scholar
  39. 39.
    Tanaka Y, Nakai M, Akahori T, Niinomi M, Tsutsumi Y, Doi H, Hanawa T. Characterization of air-formed surface oxide film on Ti–29Nb–13Ta–4.6Zr alloy surface using XPS and AES. Corros Sci. 2008;50:2111–6.CrossRefGoogle Scholar
  40. 40.
  41. 41.
    Wataha JC, Lockwood PE, Nelson SK, Bouillaguet S. Long-term cytotoxicity of dental casting alloys. Int J Prosthodont. 1999;12:242–8.Google Scholar
  42. 42.
    Owen TA, Aronov M, Shalhoub V, Barone LM, Wilming L, Tassinari MS, Kennedy MB, Pockwinse S, Lian JB, Stein GS. Progressive development of the rat osteoblast phenotype in vitro: reciprocal relationships in expression of genes associated with osteoblast proliferation and differentiation during formation of the bone extracellular matrix. J Cell Physiol. 1990;143:420–30.CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2014

Authors and Affiliations

  • Ingrid Milošev
    • 1
  • Julija Hmeljak
    • 2
  • Gregor Žerjav
    • 1
  • Andrej Cör
    • 2
  • Jose Maria Calderon Moreno
    • 3
  • Monica Popa
    • 3
  1. 1.Department of Physical and Organic ChemistryJožef Stefan InstituteLjubljanaSlovenia
  2. 2.Faculty of Health SciencesUniversity of PrimorskaIzolaSlovenia
  3. 3.Romanian Academy, Institute of Physical Chemistry “Ilie Murgulescu”BucharestRomania

Personalised recommendations