Abstract
Polyetheretherketone (PEEK) is widely used in orthopedic implants, such as spinal fusion devices, because of its moderate elastic modulus, as well as relatively high mechanical strength. However, it does not bond to living bone, and hence it needs autograft to be fixed to the bone. In this study, we attempted to add bone-bonding properties to PEEK by coating with TiO2 synthesized by the sol–gel process. When a TiO2 sol solution consisting of titanium isopropoxide, water, ethanol, and nitric acid was deposited on a PEEK substrate without any pretreatment, the formed TiO2 gel layer was easily peeled off after subsequent treatments. However, when the same solution was deposited on PEEK that was preliminarily subjected to UV or O2 plasma treatment, the deposited TiO2 gel layer strongly adhered to the substrate even after subsequent treatments. The strong adhesion was attributed to the interaction among the C–O, C=O, and O–C=O groups on the PEEK owing to the UV or O2 plasma treatment and the Ti–O bond of the TiO2 gel. Apatite did not form on the as-formed TiO2 gel layer in a simulated body fluid (SBF) even within 3 days; however, apatite formed after soaking in 0.1 M HCl solution at 80 °C for 24 h. This apatite formation was attributed to positive surface charge of the TiO2 gel layer induced by the acid treatment. The PEEK with the TiO2 gel layer coating formed by the proposed process is expected to bond to living bone, because a positively charged titanium oxide which facilitates the formation of apatite in SBF within a short period is known to bond to living bone.
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References
Skinner HB. Composite technology for total hip arthroplasty. Clin Orthop Relat Res. 1988;235:224–36.
Kurtz SM. PEEK biomaterials handbook. New York: Elsevier Science; 2011.
Briem D, Strametz S, Schröder K, Meenen NM, Lehmann W, Linhart W, Ohl A, Rueger JM. Response of primary fibroblasts and osteoblasts to plasma treated polyetheretherketone (PEEK) surfaces. J Mater Sci. 2005;16:671–7.
Pino M, Stingelin N, Tanner KE. Nucleation and growth of apatite on NaOH-treated PEEK, HDPE and UHMWPE for artificical cornea materials. Acta Biomater. 2008;4:1827–36.
Pino M, Chrzanowski W, Fabel D, Bakla M, Stingelin N, Tanner KE. Apatite deposition on NaOH-treated PEEK and UHMWPE filim for sclera materials in artificial cornea implants. Adv Eng Mater. 2010;12:B234–44.
Ha SW, Kirch M, Birchler F, Eckert KL, Mayer J, Wintermantel E, Sittig C, Pfund-Kilngenfuss I, Textor M, Spencer ND, Guecheva M, Vonmont H. Surface activation of polyetheretherketone (PEEK) and formation of calcium phosphate coatings by precipitation. J Mater Sci Mater Med. 1997;8:683–90.
Barkarmo S, Wennerberg A, Hoffman M, Kjellin P, Breding K, Handa P, Stenport V. Nano-hyroxyapatite-coated PEEK implants: a pilot study in rabbit bone. J Biomed Mater Res A. 2013;101A:465–71.
Ha SW, Mayer J, Koch B, Wintermantel E. Plasma-sprayed hydroxylapatite coating on carbon fibre reinforced thermoplastic composite materials. J Mater Sci Mater Med. 1994;5:481–4.
Ha SW, Gisep A, Mayer J, Wintermantel E, Gruner H, Wieland M. Topographical characterization and microstructural interface analysis of vacuum-plasma-sprayed titanium and hydroxyapatite coatings on carbon fibre-reinforced poly(etheretherketone). J Mater Sci Mater Med. 1997;8:891–6.
Rabiei A, Sandukas S. Processing and evaluation of bioactive coating on polymeric implants. J. Biomed Mater Res A. 2013;101A:2621–9.
Hahn B-D, Park D-S, Choi J-J, Ryu J, Yoon W-H, Choi J-H, Kim J-W, Ahn C-W, Kim H-E, Yoon B-H, Jung I-K. Osteoconductive hydroxyapatite coated PEEK for spinal fusion surgery. Appl Surf Sci. 2013;283:6–11.
Shucong Y, Hariram KP, Kurmar R, Cheang P, Aik KK. In vitro apatite formation and its growth kinetics on hydroxyapatite-polyetheretherketone biocomposites. Biomaterials. 2005;26:2343–52.
Abu Bakar MS, Cheng MHW, Tang SM, Yu SC, Liao K, Tan CT, Khor KA, Cheang P. Tensile properties, tension–tension fatigue and biological response of polyetheretherketone–hydroxyapatite composites for load-bearing orthopedic implants. Biomaterials. 2003;24:2245–50.
Tan KH, Chua CK, Leong KF, Cheah CM, Cheang P, Abu Barkar MS, Chan SW. Scafforld development using selective laser sintering of polyetheretherketon-hydroxyaopatite biocomposite blends. Biomaterials. 2003;24:3115–23.
Kim IY, Sugino A, Kikuta K, Ohtsuki T. Bioactive composites consisting of PEEK and calcium silicate powders. J Biomat Appl. 2009;24:105–18.
Tsou H-K, Hsieh PY, Chung C-J, Tang C-H, Shyr T-W, He J-L. Low-temperature deposition of anatase Titanium oxide on medical grade PEEK to assist osseous integration. Surf Coat Technol. 2009;204:1121–5.
Balas F, Kokubo T, Kawashita M, Nakamura T. Surface modification of organic polymers with bioactive titanium oxide without the aid of a silane-coupling agent. J Mater Sci Mater Med. 2007;18:1167–74.
Saito T, Takemoto M, Fukuda A, Kuroda Y, Fujibayashi S, Neo M, Honjoh D, Hiraide T, Kizuki T, Kokubo T, Nakamura T. Effect of titania-based surface modification of polyethylene terephthalate on bone-implant bonding and peri-implant tissue reaction. Acta Biomater. 2011;7:1558–69.
Kokubo T, Takadama H. How useful is SBF in predicting in vivo bone bioactivity. Biomaterials. 2006;27:2907–15.
Tsougeni K, Vourdas N, Tserepi A, Gogolides E. Mechanisms of oxygen plasma nanotexturing of organic polymer surface: from stable super hydrophilic to super hydrophobic surfaces. Langmuir. 2009;25:11748–59.
Brunette DM, Tengrall P, Textor M, Thomson P (ed.) Titanium in Medicine (Springer, Berlin, 2001).
Kokubo T, Pattanayak DK, Yamaguchi S, Takadama H, Matsushita T, Kawai T, Takemoto M, Fujibayashi S, Nakamura T. Positively charged bioactive Ti metal prepared by simple chemical and heat treatments. J R Soc Interface. 2010;7:S503–13.
Kawai T, Takemoto M, Fujibayashi S, Neo M, Akiyama H, Yamaguchi S, Pattanayak DK, Matsushita T, Nakamura T, Kokubo T. Bone-bonding properties of Ti metal subjected to acid and heat treatments. J Mater Sci. 2012;23:2981–92.
Kawai T, Takemoto M, Fujibayashi S, Akiyama H, Yamaguchi S, Pattanayak DK, Doi K, Matsushita T, Nakamura T, Kokubo T, Matsuda S. Osteoconduction of porous Ti metal enhanced by acic and heat treatments. J Mater Sci. 2013;24:1707–15.
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Kizuki, T., Matsushita, T. & Kokubo, T. Apatite-forming PEEK with TiO2 surface layer coating. J Mater Sci: Mater Med 26, 41 (2015). https://doi.org/10.1007/s10856-014-5359-1
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DOI: https://doi.org/10.1007/s10856-014-5359-1