Abstract
This chapter summarizes the state-of-the-art knowledge on the degradation modes of Ti and biomedically relevant Ti-based alloys. First, general aspects of passivity of Ti as well as special corrosion modes of passive Ti are shortly described. Then, the influence of alloying on the electrochemical dissolution modes is summarized, emphasizing the specific corrosion modes relevant for the biomedical application. Degradation of materials in biomedical applications can, in addition to purely chemical or electrochemical processes, be strongly influenced by mechanical/tribological processes. Therefore, tribocorrosion of Ti and Ti-based alloys is described. In addition, the role of the biological environment in the degradation process of Ti alloys is discussed. Moreover, a short discussion on some relevant implant design-related aspects of degradation is provided.
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References
Brunette DM, Tengvall P, Textor M, Thomsen P (eds) (2001) Titanium in medicine. Springer, New York
Tengvall P, Lundström I (1992) Physico-chemical considerations of titanium as a biomaterial. ClinMater 9:115–134
Geetha M, Singh AK, Asokami R, Gogia AK (2009) Ti based biomaterials, the ultimate choice for orthopaedic implants—a review. Prog Mater Sci 54:397–425
Schenk R (2001) The corrosion properties of titanium and titanium alloys. In: Brunette DM, Tengvall P, Textor M, Thomsen P (eds) Titanium in medicine. Springer, New York
Been J, Grauman JS (2000) Titanium and titanium alloys. In: Revie RW (ed) Uhlig’s corrosion handbook. Wiley, New York
Shoesmith DW, Noel JJ (2010) Corrosion of titanium and its alloys. In: Richardson TJA, Cottis R, Lindsay R, Stuart L, Scantlebury DJD, Graham MJ (eds) Shreir’s corrosion, vol 3. Elsevier, Oxford, UK
Long M, Rack HJ (1998) Titanium alloys in total joint replacement—a materials science perspective. Biomaterials 19:1621–1639
Niinomi M (2008) Mechanical biocompatibilities of titanium alloys for biomedical applications. J Mech Behav Biomed Mater 1:30–42
Fleck C, Eifler D (2010) Corrosion, fatigue and corrosion-fatigue behavior of metal implant materials, especially of titanium alloys. Int J Fatigue 32:929–935
Hallab NJ, Jacobs JJ (2003) Orthopedic implant fretting corrosion. Corros Rev 21:183–213
Syrett BC, Acharya A (eds) (1978) Corrosion and degradation of implant materials, ASTM STP 684. ASTM, Philadelphia
Fraker AC, Griffin CD (1985) Corrosion and degradation of implant materials, ASTM STP 859. ASTM, Philadelphia
Kovacs P, Istephanous NS (eds) (1994) Compatibility of biomedical implants, proceedings volume 94-15. The Electrochemical Society, Pennington
Pourbaix M (1963) Atlas d’Equilibres Electrochimique. Gautiers-Billars & Vie, Paris
Fovet Y, Gal J-Y, Toumelin-Chemla F (2001) Influence of pH and fluoride concentration on titanium passivating layer: stability of titanium oxide. Talanta 53:1053–1063
Robin A, Meirelis JP (2007) Influence of fluoride concentration and pH on corrosion behavior of titanium in artificial saliva. J Appl Electrochem 37:511–517
Upadhyay D, Panchal MA, Dubey RS, Srivastava VK (2006) Corrosion of alloys used in dentistry—a review. Mater Sci Eng A 432:1–11
Kelly EJ (1982) Electrochemical behavior of titanium. In: Bockris JOM, Conway BE, White RE (eds) Modern aspects of electrochemistry, No. 14, chapter 5. Plenum Press, New York
El-Taib Heakal F, Mokoda AS, Mazhar AA, El-Basiouny MS (1987) Kinetic studies on the dissolution of the anodic oxide film on titanium in phosphoric acid solutions. Corros Sci 27:453–482
Blackwood DJ, Peter LM, Williams DE (1988) Stability and open circuit breakdown of the passive oxide film on titanium. Electrochim Acta 33:1143–1149
Blackwood DJ, Greef R, Peter LM (1989) An ellipsometric study of the growth and open-circuit dissolution of the anodic oxide film on titanium. Electrochim Acta 34:875–880
Yu SY, Brodwick CW, Ryan MR, Scully JR (1999) Effects of Nb and Zr alloying additions on the activation behavior of Ti in hydrochloric acid. J Electrochem Soc 146:4429–4438
Azumi K, Nakajima M, Okamoto K, Seo M (2007) Dissolution of Ti wires in sulphuric acid and hydrochloric acid solutions. Corros Sci 49:469–480
Aladjem A (1973) Review: anodic oxidation of titanium and its alloys. J Mater Sci 8:688–704
Ghicov A, Schmuki P (2009) Self-ordering electrochemistry: a review on growth and functionality of TiO2 nanotubes and other self-aligned MOx structures. Chem Commun 20:2791–2808
Schultze JW, Lohrengel MM (2000) Stability, reactivity and breakdown of passive films. Problems of recent and future research. Electrochim Acta 45:2499–2513
Schmuki P (2002) From Bacon to barriers: a review on the passivity of metals and alloys. J Solid State Electrochem 6:145–164
Zsklarska-Smialowska Z (1986) Pitting corrosion of metals. National Association of Corrosion Engineers, Houston, TX
Dugdale I, Cotton JB (1964) The anodic polarization of titanium in halide solutions. Corros Sci 4:397–400
Beck TR (1973) Pitting of titanium. J Electrochem Soc 120:1310–1324
Rätzer-Scheibe HJ (1978) Relationship between repassivation behavior and pitting corrosion. Corrosion 34:437–442
Burstein GT, Souto RM (1995) Observations of localized instability of passive titanium in chloride solutions. Electrochim Acta 40:1881–1888
Burstein GT, Liu C, Souto RM (2005) The effect of temperature on the nucleation of corrosion pits on titanium in Ringer’s solution. Biomaterials 26:245–256
Burstein GT, Liu C (2008) Depassivation current transients measured between identical twin microelectrodes in open circuit. Corros Sci 50:2–7
Casillar N, Charlebois S, Smyrl WH (1994) Pitting corrosion of titanium. J Electrochem Soc 141:636–642
Basame SB, White HS (2000) Pitting corrosion of titanium the relationship between pitting potential and competitive anion adsorption at the oxide film/electrolyte interface. J Electrochem Soc 147:1376–1381
He X, Noel JJ, Shoesmith DW (2002) Temperature dependence of crevice corrosion initiation on titanium grade-2. J Electrochem Soc 149:B440–B449
Virtanen S (2008) Corrosion of biomedical implant materials. Corros Rev 26:147–171
Mogoda AS, Ahmad YH, Badawy WA (2004) Corrosion behavior of Ti-6Al-4V alloy in concentrated hydrochloric and sulfuric acids. J Appl Electrochem 34:873–878
Willert H-G, Brobäck L-G, Buchhorn GH, Jensen PH, Köster G, Ochsner P, Schenk R (1996) Crevice corrosion of cemented titanium alloy stems in total hip replacements. Clin Orthop Relat Res (333):51–75
Thomas SR, Shukla D, Latham PD (2004) Corrosion of cemented titanium femoral stems. J Bone Joint Surg 86-B:974–978
Kumar S, Sivakumar S, Sankara Narayanan TSN, Ganesh Sundara Raman S, Seshadri SK (2010) Fretting-corrosion mapping of CP-Ti in Ringer’s solution. Wear 268:1537–1541
Kumar S, Narayanan TSNS, Ganesh Sundara Raman S, Seshadri SK (2010) Surface modification of CP-Ti to improve the fretting-corrosion resistance: thermal oxidation vs. anodizing. Mater Sci Eng C 30:921–927
Ruzickova M, Hildebrand H, Virtanen S (2005) On the stability of passivity of Ti-Al alloys in acidic environment. Z Phys Chem 219:1447–1459
Metikos-Hukovic M, Kwokal A, Pilkac J (2003) The influence of niobium and vanadium passivity of titanium-based implants in physiological solution. Biomaterials 24:3765–3775
Milosev I, Metikos-Hukovic M, Strehblow H-H (2000) Passive film on orthopaedic TiAlV alloy formed in physiological solution investigated by X-ray photoelectron spectroscopy. Biomaterials 21:2103–2113
Milosev I, Kosec T, Strehblow H-H (2008) XPS and EIS study of the passive film formed on orthopaedic Ti-6Al-7Nb alloy in Hank’s physiological solution. Electrochim Acta 52:3547–3558
Landolt D, Mischler S, Stemp M (2001) Electrochemical methods in tribocorrosion: a critical appraisal. Electrochim Acta 46:3913–3929
Mischler S (2008) Triboelectrochemical techniques and interpretation methods in tribocorrosion: a comparative evaluation. Tribol Int 41:573–583
Khan MA, Williams RL, Williams DF (1996) In-vitro corrosion and wear of titanium alloys in the biological environment. Biomaterials 17:2117–2126
Barril S, Mischler S, Landolt D (2004) Influence of fretting regimes on the tribocorrosion behaviour of Ti6Al4V in 0.9 wt-% sodium chloride solution. Wear 256:963–972
Barril S, Mischler S, Landolt D (2005) Electrochemical effects of the fretting corrosion behavior of Ti6Al4V in 0.9 wt-% sodium chloride solution. Wear 259:282–291
Mischler S, Barril S, Landolt D (2009) Fretting corrosion behaviour of Ti-6Al-4V/PMMA contact in simulated body fluid. Tribol Mater Surf Interfaces 3:16–23
Hanawa T (2004) Metal ion release from metal implants. Mater Sci Eng C 24:745–752
Kolman DG, Scully JR (1996) On the repassivation behavior of high-purity titanium and selected α, β, and β + α alloys in aqueous chloride solutions. J Electrochem Soc 143:1847–1860
Beck TR (1973) Electrochemistry of freshly-generated titanium surface—I. Scraped-rotating-disk experiments. Electrochim Acta 18:807–814
Beck TR (1973) Electrochemistry of freshly-generated titanium surface—II. Rapid fracture experiments. Electrochim Acta 18:815–827
Buhl H (1973) Repassivation behavior of the titanium alloy TiAl6V4 in aqueous sodium halides. Corros Sci 13:639–646
Raetzer-Scheibe H-J, Buhl H (1979) Zum Repassivierungsverhalten metallischer Werkstoffe am Beispiels einer Titanlegierung—Contribution to the understanding of repassivation behavior for a titanium alloy. Werkst Korros 30:846–853
Gilbert JL, Buckley CA, Lautenschlager EP (1996) Titanium oxide film fracture and repassivation: the effect of potential, pH and aeration. In: Brown SA, Lemons JE (eds) Medical applications of titanium and its alloys: the material and biological issues, ASTM STP 1272. American Society for Testing and Materials, Philadelphia, pp 199–215
Goldberg JR, Gilbert JL (2004) The electrochemical and mechanical behavior of passivated and TiN/AlN-coated CoCrMo and Ti6Al4V alloys. Biomaterials 25:851–864
Lausmaa J (1996) Surface spectroscopic characterization of titanium implant materials. J Electron Spectrosc Rel Phen 31:343–361
Sittig C, Hähner G, Marti A, Textor M, Spencer ND, Hauert R (1999) The implant material, Ti6Al7Nb: surface microstructure, composition and properties. J Mater Sci Mater Med 10:191–198
Schuh A, Bigoney J, Hönle W, Zeiler G, Holzwarth U, Forst R (2007) Second generation (low modulus) titanium alloys in total hip arthoplasty. Materialwiss Werkst 38:1003–1007
Guillemot F (2005) Recent advances in the design of titanium alloys for orthopedic applications. Exp Rev Med Dev 2:741–748
Davidson JA, Mishra AK, Kovacs P, Poggie RA (1994) New surface-hardened, low-modulus, corrosion-resistant Ti13Nb13Zr alloy for total hip arthoplasty. Biomed Mater Eng 4:231–243
Niinomi M (2003) Fatigue performance and cyto-toxicity of low rigidity titanium alloys Ti-29Nb-13Ta-4.6Zr. Biomaterials 24:2673–2683
Yu SY, Scully JR (1997) Corrosion and passivity of Ti-13%Nb-13%Zr in comparison to other biomedical implant alloys. Corrosion 53:965–976
Robin A, Carvalho OAS, Schneider SG, Schneider S (2008) Corrosion behavior of Ti-xNb-13Zr alloys in Ringer’s solution. Mater Corros 59:929–933
Khan MA, Williams RL, Williams DF (1999) Conjoint corrosion and wear in titanium alloys. Biomaterials 20:765–772
Akahori T, Niinomi M, Fukui H, Suzuki A (2004) Fatigue, fretting fatigue and corrosion characteristics of biocompatible beta type titanium alloy conducted with various thermo-mechanical treatments. Mater Trans 45:1540–1548
Zhoua YL, Niinomi M, Akahori T, Fukui H, Toda H (2005) Corrosion resistance and biocompatibility of Ti-Ta alloys for biomedical applications. Mater Sci Eng A 398:28–36
Virtanen S, Milosev I, Gomez-Barrena E, Trebse R, Salo J, Konttinen YT (2008) Special modes of corrosion under physiological and simulated physiological conditions. Acta Biomater 4:468–476
Hiromoto S, Hanawa T (2006) Corrosion of implant metals in the presence of cells. Corros Rev 24:323–352
Galante JO, Lemons J, Spector M, Wilson PD Jr, Wright TM (1991) Review. The biologic effect of implant materials. J Orthop Res 9:760–775
Bundy KJ (1994) Corrosion and other electrochemical aspects of biomaterials. Crit Rev Biomed Eng 22:139–251
Mathew MT, Srinisiva Pai P, Pourzal R, Fischer A, Wimmer MA (2009) Significance of tribocorrosion in biomedical applications: overview and current status. Adv Tribol; article no. 250986
Cadosch D, Chan E, Gautschi OP, Filgueira L (2009) Metal is not inert: role of metal ions released by biocorrosion in aseptic loosening—current concepts. J Biomed Mater Res 91A:1252–1262
Alves VA, Reis RQ, Santos ICB, Souza DG, de F Goncalves T, Pereira-da-Silva MA, Rossi A, da Silva LA (2009) In situ impedance spectroscopy study of the electrochemical corrosion of Ti and Ti-6Al-4V in simulated body fluid at 25°C and 37°C. Corros Sci 51:2473–2482
Hodgson AWE, Mueller Y, Forster D, Virtanen S (2002) Electrochemical characterization of passive film on Ti alloys under simulated biological conditions. Electrochim Acta 47:1913–1923
Hanawa T, Ota M (1991) Calcium phosphate naturally formed on titanium in electrolyte solution. Biomaterials 12:767–774
Sousa SR, Barbosa MA (1993) Corrosion resistance of titanium cp in saline physiological solution with calcium phosphate and proteins. Clin Mater 14:287–294
Wu W, Nancollas GH (1998) Kinetics of heterogeneous nucleation of calcium phosphates on anatase and rutile. J Colloid Interface Sci 199:206–211
Li P, Ducheyne P (1998) Quasi-biological apatite film induced by titanium in a simulated body fluid. J Biomed Mater Res 41:341–348
Frauchiger L, Taborelly M, Aronsson BO, Descouts P (1999) Ion adsorption on titanium surfaces exposed to a physiological solution. Appl Surf Sci 143:57–77
Healy KE, Ducheyne P (1992) Hydration and preferential molecular adsorption on titanium in vitro. Biomaterials 13:553–561
Sundgren JE, Bodo P, Lundstrom I (1986) Auger electron spectroscopic study of the interface between human tissue and implants of titanium and stainless steel. J Colloid Interface Sci 110:9–20
Lima J, Sousa SR, Ferreira A, Barbosa MA (2001) Interactions between calcium, phosphate, and albumin on the surface of titanium. J Biomed Mater Res 55:45–53
Ban S, Maruno S (1995) Effect of temperature on electrochemical deposition of calcium phosphate coatings in a simulated body fluid. Biomaterials 16:977–981
Eliaz N, Kopelovitch W, Burstein L, Kobayashi E, Hanawa T (2008) Electrochemical processes of nucleation and growth of calcium phosphate on titanium supported by real-time quartz crystal microbalance measurements and X-ray photoelectron spectroscopy analysis. J Biomed Mater Res 89A:270–280
Narayanan R, Seshadri SK, Kwon TY, Kim KH (2008) Calcium phosphate-based coatings on titanium and its alloys. J Biomed Mater Res B 85:279–299
Cheng R, Roscoe SG (2005) Corrosion behavior of titanium in the presence of calcium phosphate and serum proteins. Biomaterials 26:7350–7356
Alkhateeb E, Virtanen S (2005) Influence of surface self-modification in Ringer’s solution on the passive behavior of titanium. J Biomed Mater Res A 75:934–940
Hanawa T, Asami K, Asaoka K (1998) Repassivation of titanium and surface oxide film regenerated in simulated bioliquid. J Biomed Mater Res 40:530–538
Clark GCF, Williams DF (1982) The effects of proteins on metallic corrosion. J Biomed Mater Res 16:125–134
Williams RL, Brown SA, Merritt K (1988) Electrochemical studies on the influence of proteins on the corrosion of implant alloys. Biomaterials 9:181–186
Burgos-Asperilla L, Garcia-Alonso MC, Escudero ML, Alonso C (2010) Study of the interaction of inorganic and organic compounds of cell culture medium with a Ti surface. Acta Biomater 6:652–661
Ehrenberger MT, Gilbert JL (2010) The effect of scanning electrochemical potential on the short-term impedance of commercially pure titanium in simulated biological conditions. J Biomed Mater Res 94A:781–789
Khan MA, Williams RL, Williams DF (1999) The corrosion behavior of Ti-6Al-4V, Ti-6Al-7Nb and Ti-13Nb-13Zr in protein solutions. Biomaterials 20:631–637
Hanawa T, Kohayama Y, Hiromoto S, Yamamoto A (2004) Effects of biological factors on the repassivation current of titanium. Mater Trans 45:1635–1639
Hiromoto S, Mischler S (2006) The influence of proteins on the fretting-corrosion behavior of a Ti6Al4V alloy. Wear 261:1002–1011
Mu Y, Kobayashi T, Sumita M, Yamamoto Y, Hanawa T (2000) Metal ion release from titanium with active oxygen species generated by rat macrophages in vitro. J Biomed Mater Res 49:238–243
Lin H-Y, Bumgardner JL (2004) In vitro biocorrosion of Ti-6Al-4V implant alloy by a mouse macrophage cell line. J Biomed Mater Res 68A:717–724
Lin H-Y, Bumgardner JL (2004) Changes in the surface composition of the Ti-6Al-4V implant alloy by cultured macrophage cells. Appl Surf Sci 225:21–28
Hiromoto S, Noda K, Hanawa T (2002) Development of electrolytic cell with cell-culture for metallic biomaterials. Corros Sci 44:955–965
Hiromoto S, Noda K, Hanawa T (2002) Electrochemical properties of an interface between titanium and fibroblasts L929. Electrochim Acta 48:387–396
Garcia-Alonso MC, Saldana L, Alonso C, Barranco V, Munoz-Morris MA, Escudero ML (2009) In situ cell culture monitoring on a Ti-6Al-4V surface by electrochemical techniques. Acta Biomater 5:1374–1384
Hiromoto S, Hanawa T, Asami K (2004) Composition of surface oxide films of titanium with culturing murine fibroblasts L929. Biomaterials 25:979–986
Hiromoto S, Hanawa T (2004) pH near cells on stainless steel and titanium. Electrochem Solid State Lett 7:B9–B11
Tengvall P, Elwing H, Sjöqvist L, Lundström I (1989) Interaction between hydrogen peroxide and titanium: a possible role in the biocompatibility of titanium. Biomaterials 10:118–120
Pan J, Thierry D, Leygraf C (1996) Hydrogen peroxide toward enhanced oxide growth on titanium in PBS solution: blue coloration and clinical relevance. J Biomed Mater Res 30:393–402
Pan J, Liao H, Leygraf C, Thierry D, Li J (1998) Variation of oxide films on titanium induced by osteoblast-like cell culture and the influence of an H2O2 pretreatment. J Biomed Mater Res 40:244–256
Bearinger JP, Orme CA, Gilbert JL (2003) Effect of hydrogen peroxide on titanium surface: in situ imaging and step-polarization impedance spectroscopy of commercially pure titanium and titanium, 6-aluminum,4-vanadium. J Biomed Mater Res 67A:702–712
Virtanen S, Isaacs HS, Schmuki P (2002) In situ X-ray absorption near edge studies of mechanisms of passivity. Electrochim Acta 47:3117–3125
Tsaryk R, Kalbacova M, Hempel U, Scharnweber D, Unger RE, Dieter P, Kirkpatrick CJ, Peters K (2007) Response of human endothelial cells to oxidative stress on Ti6Al4V alloy. Biomaterials 28:806–813
Ehrensberger MT, Sivan S, Gilbert JL (2009) Titanium is not “the most biocompatible metal” under cathodic potential: the relationship between voltage and MC3T3 preosteoblast behavior on electrically polarized cpTi surfaces. J Biomed Mater Res 93A:1500–1509
Serhan H, Slivka M, Albert T, Kwak SD (2004) Is galvanic corrosion between titanium alloy and stainless steel spinal implant a clinical concern? Spine J 4:379–387
Mueller Y, Tognini R, Mayer J, Virtanen S (2007) Anodized titanium and stainless steel in contact with CFRP: an electrochemical approach considering galvanic corrosion. J Biomed Mater Res 82A:936–946
Marek M, Pawar V, Tsai S, Thomas R, Sprague J, Salehi A, Hunter G (2006) Galvanic corrosion evaluation of Zr-25Nb coupled with orthopaedic alloys. In: Medical device materials III, vol 2006., pp 195–201
Griffin CD, Buchanan RA, Lemons JE (1983) In vitro electrochemical corrosion study of coupled surgical implant materials. J Biomed Mater Res 17:489–500
Konttinen YT, Takagi M, Mandelin J, Lassus J, Salo J, Ainola M (2001) Acid attack and cathepsin K in bone resorption around total hip replacements. J Bone Miner Res 16:1780–1786
Schöll E, Eggli S, Ganz R (2000) Osteolysis in cemented titanium alloy hip prosthesis. J Arthoplasty 15:570–575
Kovac S, Trebse R, Milosev I, Pavlovcic V, Pisot V (2006) Long-term survival of a cemented titanium-aluminum-vanadium alloy straight-stem femoral component. J Bone Joint Surg 88:1567–1573
Paliwal M, Gordon Allan D, Filip P (2010) Failure analysis of three uncemented titanium-alloy modular total hip stems. Eng Fail Anal 17:1230–1238
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Virtanen, S. (2012). Degradation of Titanium and Its Alloys. In: Eliaz, N. (eds) Degradation of Implant Materials. Springer, New York, NY. https://doi.org/10.1007/978-1-4614-3942-4_2
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