Effect of pulse current on structure and adhesion of apatite electrochemically deposited onto titanium substrates


Apatite films were deposited onto titanium (Ti) metal substrates by an electrodeposition method under a pulse current. Metastable calcium phosphate solution was used as the electrolyte. The ion concentration of the solution was 1.5 times that of human body fluid, but the solution did not contain magnesium ions at 36.5 °C. We used an average current density of 0.01 A/cm2 and current-on time (TON) equal to current-off time (TOFF) of 10 ms, 100 ms, 1 s, and 15 s. The adhesive strength between apatite and Ti substrates were relatively high at TON = TOFF = 10 ms. It is considered that small calcium phosphate (C–P) crystals with low crystallinity were deposited on the Ti surface without reacting with other C–P crystals, H2O, and HCO3 in the surrounding environment. This resulted in relaxation of the lattice mismatch and enhancement of the adhesive strength between the apatite crystals and Ti substrates.

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  1. 1

    H.B. Wen, J.R. de Wijin, F.Z. Cui, K. de Groot: Preparation of bioactive Ti6A14V surfaces by a simple method. Biomaterials 19, 215 1998

    CAS  Article  Google Scholar 

  2. 2

    Y. Okazaki, E. Nishimura, E. Nakada, K. Kobayashi: Surface analysis of Ti–15Zr–4Nb–4Ta alloy after implantation in rat tibia. Biomaterials 22, 599 2001

    CAS  Article  Google Scholar 

  3. 3

    Y. Okazaki, S. Rao, Y. Ito, T. Tateishi: Corrosion resistance, mechanical properties, corrosion fatigue strength and cytocompatibility of new Ti alloys without Al and V. Biomaterials 19, 1197 1998

    CAS  Article  Google Scholar 

  4. 4

    U. Rolander, L. Mattsson, J. Lausmaa, B. Kasemo: Anodic oxide films on titanium. Ultramicroscopy 19, 407 1986

    Article  Google Scholar 

  5. 5

    H. Kienapfel, C. Sprey, A. Wilke, P. Griss: Implant fixation by bone ingrowth. J. Arthrop. 14, 355 1999

    CAS  Article  Google Scholar 

  6. 6

    T. Kitsugi, T. Nakamura, M. Oka, Y. Senaha, T. Goto, T. Shibuya: Bone-bonding behavior of plasma-sprayed coatings of Bioglass®, AW-glass ceramic, and tricalcium phosphate on titanium alloy. J. Biomed. Mater. Res. 30, 261 1996

    CAS  Article  Google Scholar 

  7. 7

    F. Barrere, C.A. Vanbitterswijk, K. Degroot, P. Layrolle: Nucleation of biomimetic Ca–P coatings on Ti6Al4V from a SBF×5 solution: Influence of magnesium. Biomaterials 23, 2211 2002

    CAS  Article  Google Scholar 

  8. 8

    T. Miyazaki, C. Ohtsuki, Y. Akioka, M. Tanihara, J. Nakao, Y. Sakaguchi, S. Konagaya: Apatite deposition on polyamide films containing carboxyl group in a biomimetic solution. J. Mater. Sci.-Mater. Med. 14, 569 2003

    CAS  Article  Google Scholar 

  9. 9

    S. Ban, J. Hasegawa: Morphological regulation and crystal growth of hydrothermal-electrochemically deposited apatite. Biomaterials 23, 2965 2002

    CAS  Article  Google Scholar 

  10. 10

    A. Stoch, A. Brożek, G. Kmita, J. Stoch, W. Jastrzębski, A. Rakowska: Electrophoretic coating of hydroxyapatite on titanium implants. J. Mol. Struct. 596, 191 2001

    CAS  Article  Google Scholar 

  11. 11

    L.A. Sena, M.C. Andrade, A.M. Rossi, G.A. Soares: Hydroxyapatite deposition by electrophoresis on titanium sheets with different surface finishing. J. Biomed. Mater. Res. A 60, 1 2002

    Article  Google Scholar 

  12. 12

    Y. Fu, A.W. Batchelor, Y. Wang, K.A. Khor: Fretting wear behaviors of thermal sprayed hydroxyapatite (HA) coating under unlubricated conditions. Wear 217, 132 1998

    CAS  Article  Google Scholar 

  13. 13

    Y. Fu, A.W. Batchelor, K.A. Khor: Fretting wear behavior of thermal sprayed hydroxyapatite coating lubricated with bovine albumin. Wear 230, 98 1999

    CAS  Article  Google Scholar 

  14. 14

    H.C. Gledhill, I.G. Turner, C. Doyle: In vitro fatigue behaviour of vacuum plasma and detonation gun sprayed hydroxyapatite coatings. Biomaterials 22, 1233 2001

    CAS  Article  Google Scholar 

  15. 15

    M. Manso, C. Jimenez, C. Morant, P. Herrero, J.M. Martinez-Duart: Electrodeposition of hydroxyapatite coatings in basic conditions. Biomaterials 21, 1775 2000

    Article  Google Scholar 

  16. 16

    M. Kawashita, S. Itoh, K. Miyamoto, G.H. Takaoka: Apatite formation on titanium substrates by electrochemical deposition in metastable calcium phosphate solution. J. Mater. Sci.-Mater. Med. 19, 137 2008

    CAS  Article  Google Scholar 

  17. 17

    S. Ban: Development of electrochemical apatite-coating on titanium for biological application. Phos. Res. Bull. 17, 9 2004

    CAS  Article  Google Scholar 

  18. 18

    S. Ban, S. Maruno: Effect of pH buffer on electrochemical deposition of calcium phosphate. Jpn. J. Appl. Phys. 32, 1577 1993

    Article  Google Scholar 

  19. 19

    M. Kawashita, T. Hayakawa, G.H. Takaoka: Electrochemical deposition of apatite on titanium substrates by using pulse current. Key Eng. Mater. 361–363, 629 2008

    Google Scholar 

  20. 20

    T. Hayakawa, M. Kawashita, G.H. Takaoka: Coating of hydroxyapatite films on titanium substrates by electrodeposition under pulse current. J. Ceram. Soc. Jpn. 116, 68 2008

    CAS  Article  Google Scholar 

  21. 21

    D.T. Zero, G. Cavaretta Siegel, J. Fu, H. Li: Effect of pyrophosphate on fluoride enhanced remineralization after an erosive challenge. Caries Res. 34, 344 2000

    Google Scholar 

  22. 22

    T. Kokubo, H. Kushitani, S. Sakka, T. Kitsugi, T. Yamamuro: Solutions able to reproduce in vivo surface-structure changes in bioactive glass-ceramic A-W. J. Biomed. Mater. Res. 24, 721 1990

    CAS  Article  Google Scholar 

  23. 23

    N.C. Blumenthal: Mechanisms of inhibition of calcification. Clin. Orthop. Relat. Res. 247, 279 1989

    Google Scholar 

  24. 24

    S. Ban, Y. Iwaya, H. Kono, H. Sato: Surface modification of titanium by etching in concentrated sulfuric acid. Dent. Mater. 22, 1115 2006

    CAS  Article  Google Scholar 

  25. 25

    S. Ban, S. Maruno: Morphology and microstructure of electrochemically deposited calcium phosphates in a modified simulated body fluid. Biomaterials 19, 1245 1998

    CAS  Article  Google Scholar 

  26. 26

    H.P. Klug, L.E. Alexander: X-ray Diffraction Procedures 2nd ed. Wiley & Sons Inc. New York 1974 505–565

    Google Scholar 

  27. 27

    H. Monma: Electrolytic depositions of calcium phosphates on substrate. J. Mater. Sci. 29, 949 1994

    CAS  Article  Google Scholar 

  28. 28

    C. Rey, B. Collins, T. Goehl, I.R. Dickson, M.J. Glimcher: The carbonate environment in bone mineral: A resolution-enhanced Fourier transform infrared spectroscopy study. Calcif. Tissue Int. 45, 157 1989

    CAS  Article  Google Scholar 

  29. 29

    B.O. Fowler, E.C. Moneno, W.E. Brown: Infra-red spectra of hydroxyapatite, octacalcium phosphate and pyrolysed octacalcium phosphate. Arch. Oral Biol. 11, 477 1966

    CAS  Article  Google Scholar 

  30. 30

    Y. Nonaka, Y. Morimoto: Characteristic and applications of amorphous chromium plating. J. Surface Finish. Soc. Jpn. 56, 329 2005

    CAS  Article  Google Scholar 

  31. 31

    J. Yamazaki, T. Kuranaga, H. Takaba, N. Saito, Y. Inoue, O. Takai: Electrochromic response of obliquely sputtered InN films. J. Surface Finish. Soc. Jpn. 57, 459 2006

    CAS  Article  Google Scholar 

  32. 32

    S. Lin, R.Z. LeGeros, J.P. LeGeros: Adherent octacalciumphosphate coating on titanium alloy using modulated electrochemical deposition method. J. Biomed. Mater. Res. A 66, 819 2003

    Article  Google Scholar 

  33. 33

    S. Haruyama: Electrochemistry for Surface Engineers 2nd ed. Maruzen Tokyo 2005 171 in Japanese

    Google Scholar 

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This work was partially supported by Funds for Promoting Science and Technology under the Program for Exploring Advanced Interdisciplinary Frontiers, the Ministry of Education, Culture, Sports, Science and Technology, Japan.

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Correspondence to Masakazu Kawashita.

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Hayakawa, T., Kawashita, M., Takaoka, G.H. et al. Effect of pulse current on structure and adhesion of apatite electrochemically deposited onto titanium substrates. Journal of Materials Research 23, 3176–3183 (2008). https://doi.org/10.1557/JMR.2008.0386

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