Initial formation kinetics of calcium phosphate on titanium in Hanks' solution characterized using XPS

One cause of the excellent hard‐tissue compatibility of Ti and Ti alloys compared with other metals is their ability to form calcium phosphate in biological environments. This is confirmed by many studies, although the formation mechanism has not been completely elucidated. In this study, to elucidate the initial formation kinetics of calcium phosphate on Ti in the human body, Ti was immersed in a simulated body fluid, Hanks' solution, for 100–106 s, followed by precise characterization using XPS. Ti specimens immersed in diluted Hanks' solutions were also characterized. The results reveal that phosphate ions are preferentially adsorbed and are incorporated onto the Ti surface in 100–102 s. This reaction is slow, and the apparent thickness of the surface layer is almost constant as 5.2 nm until 102 s. However, both calcium and phosphate ions are then rapidly incorporated, and calcium phosphate is formed after 103 s. The amounts of both calcium and phosphate increase with the logarithm of time because calcium and phosphate ions react directly with the Ti surface until 105 s. Other elements contained in Hanks' solution are not incorporated, calcium phosphate being formed preferentially. The incorporation of calcium is faster than that of phosphate, and the [Ca]/[P] ratio increases with the logarithm of time after 103 s. However, the chemical state of surface oxide film itself on Ti does not changed by immersion in Hanks' solution. The formation kinetics of calcium phosphate on Ti in a simulated body fluid are clearly revealed by this study.

[1]  J. Vazquez-Arenas,et al.  XPS and EIS studies to account for the passive behavior of the alloy Ti-6Al-4V in Hank’s solution , 2019, Journal of Solid State Electrochemistry.

[2]  T. Hanawa Titanium–Tissue Interface Reaction and Its Control With Surface Treatment , 2019, Front. Bioeng. Biotechnol..

[3]  W. Harun,et al.  A comprehensive review of hydroxyapatite-based coatings adhesion on metallic biomaterials , 2018 .

[4]  M. Thuvander,et al.  The bone-implant interface of dental implants in humans on the atomic scale. , 2017, Acta biomaterialia.

[5]  Ke Wang,et al.  Local Fine Structural Insight into Mechanism of Electrochemical Passivation of Titanium. , 2016, ACS applied materials & interfaces.

[6]  Y. Tsutsumi,et al.  Reaction of calcium and phosphate ions with titanium, zirconium, niobium, and tantalum , 2015 .

[7]  Y. Tsutsumi,et al.  Calcium Phosphate Formation on Titanium and Zirconium and Its Application to Medical Devices , 2010 .

[8]  N. Nomura,et al.  Difference in surface reactions between titanium and zirconium in Hanks' solution to elucidate mechanism of calcium phosphate formation on titanium using XPS and cathodic polarization , 2009 .

[9]  Y. Tsutsumi,et al.  Characterization of air-formed surface oxide film on Ti–29Nb–13Ta–4.6Zr alloy surface using XPS and AES , 2008 .

[10]  Tadashi Kokubo,et al.  How useful is SBF in predicting in vivo bone bioactivity? , 2006, Biomaterials.

[11]  T. Hanawa,et al.  Composition of surface oxide film of titanium with culturing murine fibroblasts L929. , 2004, Biomaterials.

[12]  S. Virtanen,et al.  Electrochemical characterisation of passive films on Ti alloys under simulated biological conditions , 2002 .

[13]  P. Descouts,et al.  Ion adsorption on titanium surfaces exposed to a physiological solution , 1999 .

[14]  T. Hanawa,et al.  Repassivation of titanium and surface oxide film regenerated in simulated bioliquid. , 1998, Journal of biomedical materials research.

[15]  Rickard Brånemark,et al.  Biomechanical characterization of osseointegration: An experimental in vivo investigation in the beagle dog , 1998, Journal of orthopaedic research : official publication of the Orthopaedic Research Society.

[16]  B. Saramago,et al.  Apatite deposition on titanium surfaces--the role of albumin adsorption. , 1997, Biomaterials.

[17]  H. M. Kim,et al.  Preparation of bioactive Ti and its alloys via simple chemical surface treatment. , 1996, Journal of biomedical materials research.

[18]  D. Thierry,et al.  Hydrogen peroxide toward enhanced oxide growth on titanium in PBS solution: blue coloration and clinical relevance. , 1996, Journal of biomedical materials research.

[19]  P. Ducheyne,et al.  The mechanisms of passive dissolution of titanium in a model physiological environment. , 1992, Journal of biomedical materials research.

[20]  T. Hanawa,et al.  Calcium phosphate naturally formed on titanium in electrolyte solution. , 1991, Biomaterials.

[21]  J. Ellingsen,et al.  A study on the mechanism of protein adsorption to TiO2. , 1991, Biomaterials.

[22]  H. Sudo,et al.  Osteocompatibility of platinum-plated titanium assessed in vitro. , 1989, Biomaterials.

[23]  Ingemar Lundström,et al.  Auger electron spectroscopic studies of the interface between human tissue and implants of titanium and stainless steel , 1986 .

[24]  T. Masumoto,et al.  Electrochemical and XPS Studies on Corrosion Behavior of Amorphous Ni-Cr-P-B alloys , 1977 .

[25]  D. A. Shirley,et al.  High-Resolution X-Ray Photoemission Spectrum of the Valence Bands of Gold , 1972 .

[26]  H. Boehm.,et al.  Functional Groups on the Surfaces of Solids , 1966 .

[27]  J. W. Ross,et al.  On the Standard Potential of the Titanium(III)-Titanium(II) Couple , 1963 .

[28]  S. Spriano,et al.  SURFACE MODIFICATION OF METALLIC BIOMATERIALS , 2005 .

[29]  Marcus Textor,et al.  Titanium in Medicine : material science, surface science, engineering, biological responses and medical applications , 2001 .

[30]  J. Hirsch,et al.  Surface analysis of failed oral titanium implants. , 1999, Journal of biomedical materials research.

[31]  T. Hanawa,et al.  Structure of Surface-Modified Layers of Calcium-Ion-Implanted Ti–6Al–4V and Ti–56Ni , 1995 .

[32]  D. Thierry,et al.  Electrochemical and XPS studies of titanium for biomaterial applications with respect to the effect of hydrogen peroxide. , 1994, Journal of biomedical materials research.

[33]  H. Habazaki,et al.  The surface characterization of titanium and titanium-nickel alloys in sulfuric acid , 1993 .

[34]  T. Hanawa,et al.  Characterization of surface film formed on titanium in electrolyte using XPS , 1992 .

[35]  H. Habazaki,et al.  A photoelectrochemical and ESCA study of passivity of amorphous nickel-valve metal alloys , 1990 .

[36]  Hideaki Takahashi,et al.  Surface films formed on aluminum by different pretreatments. I. XPS analysis of thickness and chemical composition. , 1985 .

[37]  K. Asami,et al.  An XPS study of the surfaces on Fe-Cr, Fe-Co and Fe-Ni alloys after mechanical polishing , 1984 .

[38]  E. Kelly Electrochemical Behavior of Titanium , 1982 .

[39]  R. Dickie,et al.  The application of x-ray photo-electron spectroscopy to a study of interfacial composition in corrosion-induced paint de-adhesion , 1981 .

[40]  K. Asami,et al.  XPS determination of compositions of alloy surfaces and surface oxides on mechanically polished iron-chromium alloys , 1977 .

[41]  K. Asami,et al.  The X-ray photo-electron spectra ofseveral oxides of iron and chromium , 1977 .

[42]  G. D. Parfitt The Surface of Titanium Dioxide , 1976 .

[43]  K. Asami A precisely consistent energy calibration method for X-ray photoelectron spectroscopy , 1976 .

[44]  C. R. Brundle The application of electron spectroscopy to surface studies , 1974 .

[45]  H. Boehm.,et al.  Acidic and basic properties of hydroxylated metal oxide surfaces , 1971 .