Characterization and Corrosion Behavior of Hydroxyapatite- Coated Titanium Substrates Prepared Through Laser Induced Liquid Deposition Technique


Nanotechnology and Advanced Materials, Material and Energy Research Center(MERC)


Titanium and titanium alloys are often used in orthopedic surgery and dentistry because of their especial characteristics such as biocompatibility, mechanical properties, and corrosion resistance. However, their bio- inertness is the most serious drawback for biomedical applications. Therefore, a bioactive coating like hydroxyapatite (HA) is coated on their surface. In this regard, in the present study, laser induced liquid deposition (LLD) technique was used to deposit nanocrystalline HA films on titanium substrates at room temperature and various exposure times (20, 30, and 60 min) were examined. The LLD method was employed via applying a laser irradiation into a liquid precursor and depositing the HA films on titanium substrates immersed in the liquid precursor. Materials characterization was examined by X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM) equipped Electron Dispersive X-ray (EDX). Also, corrosion behaviors of coating were evaluated by potentiodynamic polarization test in simulated body fluid (SBF). Results showed that by choosing the appropriate exposure time, the corrosion resistance of coated substrates improves by HA coatings versus uncoated Ti substrates.


Main Subjects

1. Verne, E., Fernandez, C.V., Brovarone, C.V., Spriano, S., Moisescu, C., “Double-layer glass-ceramic coatings on Ti6Al4V for dental implants”, Journal of the European Ceramic Society, Vol. 24, (2004), 2699–2705.
2. Floroian, L., Sima, F., Florescu, M., Badea, M., Popescu, A.C., Serban, N., Mihailescu, I.N., “Double layered nanostructured composite coatings with bioactive silicate glass and polymethylmetacrylate for biomimetic implant applications”, Journal of Electroanalytical Chemistry, Vol. 648, (2010), 111- 118.
3. Schrooten, J., Helsen, J.A., “Adhesion of bioactive glass coating to Ti6Al4V oral implant”, Biomaterials, Vol. 21, (2000), 1461-1469.
4. Xiao, Y., Song, L., Liu, X., Huang, Y., Huang, T., Wu, Y., Chen, J., Wu, F., “Nanostructured bioactive glass–ceramic coatings deposited by the liquid precursor plasma spraying process”, Applied Surfuce Science, Vol. 257, (2011), 1898– 1905.
5. Balamurugan, A., Balossier, G., Michel, J., Ferreira, J.M.F., “Electrochemical and structural evaluation of functionally graded bioglass-apatite composites electrophoretically deposited onto Ti6Al4V alloy”, Electrochimca Acta, Vol. 54, (2009), 1192–1198.
6. Jurczyk, M., “Bionanomaterials for Dental Applications”, Pan Stanford Publishing Pte Ltd, (2013).
7. Okazaki,Y., Emiko, G., “Comparison of metal release from various metallic biomaterials in vitro”, Biomaterials, Vol. 26, (2005), 11-21.
8. Geetha, M., Singh, A.K., Asokamani, R., Gogia, A.K., “Ti based biomaterials, the ultimate choice for orthopedic implantsa review”, Progress in Materials Science, Vol. 54, 2009, 397– 425.
9. Singh, R., Dahotre, N.B., “Corrosion degradation and prevention by surface modification of biometallic materials”, J Mater Sci: Mater Med, Vol. 18, (2007), 725–751.
10. Garcia, C., Cere, S., Duran, A., “Bioactive coatings deposited on titanium alloys”, Journal of Non-Crystalline Solids, Vol. 352, (2006), p 3488–3495.
11. Monsalve, M., Ageorges, H., Lopez, E., Vargas, F., Bolivar, F., “Bioactivity and mechanical properties of plasma-sprayed coatings of bioglass powders”, Surface Coating Technology, (2013), 220, 60–66.
12. Soundrapandian, C., Bharati, S., Basu, D., Datta, S., “Studies on novel bioactive glasses and bioactive glass–nano-Hap composites suitable for coating on metallic implants”, Ceramics International, Vol. 37, (2011), 759–769.
13. Plewinski, M., Schickle, K., Lindner, M., Kirsten, A., Weber, M., Fischer, H., “The effect of crystallization of bioactive bioglass 45S5 on apatite formation and degradation”, Dental Materials, Vol. 29, 2013, 1256-1264.
14. Stan, G.E., and Ferreira, J.M.F., “Magnetron sputtered BG thin films: an alternative biofunctionalization approachpeculiarities of bioglass sputtering and bioactivity behavior”, In Feng Shi (ed.) Ceramic Coatings- Applications in Engineering, (2012), 71-98.
15. Ravarian, R., Moztarzadeh, F., Hashjin, M.S., Rabiee, S.M., Khoshakhlagh, P., Tahriri, M., “Characterization and bioactivity investigation of bioglass/hydroxyapatite composite”, Ceramics International, Vol. 36, (2010), 291–297.
16. Martínez-Castañón, G.A., Loyola-Rodríguez, J.P., Zavala- Alonso, N.V., Hernández-Martínez, S.E., Niño-Martínez, N., Ortega-Zarzosa, G., Ruiz, F., “Preparation and characterization of nanostructured powders of hydroxyapatite”, Superficies y Vacío, Vol. 25, (2012), 101-105.
17. Han, Y.J., Loo, S.C.J., Lee, J. and Ma, J., “Investigation of the bioactivity and biocompatibility of different glass interfaces with hydroxyapatite, fluorohydroxyapatite and 58S bioactive glass”, BioFactors, vol. 30, (2007), 205–216.
18. Angelescu, N., Ungureanu, D.N., Anghelina, F.V., “Synthesis and characterization of hydroxyapatite obtained in different experimental conditions”, The Scientific Bulletin Of Valahia University; Materials And Mechanics, Vol. 1, (2011), 15-18.
19. Arsad, M.S.M., Lee, P.M., Hung, L.K., “Synthesis and characterization of hydroxyapatite nanoparticles and β-tcp particles”, Proc. 2nd International Conference on Biotechnology and Food Science, Singapore, (2011).
20. Choi, J.M., Kim, H.E., Lee, I.S., “Ion-beam-assisted deposition (IBAD) of hydroxyapatite coating layer on Ti-based metal substrate”, Biomaterials, Vol. 21, (2000), 469-473.
21. Koch, C.F., Johnson, S., Kumar, D., Jelinek, M., Chrisey, D.B., Doraiswamy, A., Jin, C., Narayan, R.J., Mihailescu, I.N., “Pulsed laser deposition of hydroxyapatite thin films”, Materials Science And Engineering: C, Vol. 27, (2007), 484- 494.
22. Kuo, M.C., Yen, S.K., “The process of electrochemical deposited hydroxyapatite coatings on biomedical titanium at room temperature”, Materials Science And Engineering: C, Vol. 20, (2002), 153-160.
23. Kwok, C.T., Wong, P.K., Cheng, F.T., Man, H.C., “Characterization and corrosion behavior of hydroxyapatite coatings on Ti6Al4V fabricated by electrophoretic deposition”, Applied Surface Science, Vol. 255, (2009), 6736-6744.
24. Metikos-Hukovic, M., Tkalcec, E., Kwokal, A., Piljac, J., “An in vitro study of Ti and Ti-alloys coated with sol–gel derived hydroxyapatite coatings”, Surface and Coatings Technology, Vol. 165, (2003), 40–50.
25. Gua, Y.W., Khor, K.A., Cheang, P., “In vitro studies of plasmasprayed hydroxyapatite/Ti-6Al-4V composite coatings in simulated body fluid (SBF)”, Biomaterials, Vol. 24, (2003), 1603–1611.
26. Ding, S., Ju, C., Lin, J.C., “Immersion behavior of RF magnetron-assisted sputtered hydroxyapatite/titanium coatings in simulated body fluid”, Journal of Biomedical Materials Research A, Vol. 47, (1999), 551-563.
27. Yuan-Yuan, Z., Jie, T., Ying-Chun, P., Wei, W., Tao, W., “Electrochemical deposition of hydroxyapatite coatings on titanium”, Transactions of Nonferrous Metals Society of China, Vol. 16, (2006), 633-637.
28. Ferro, D., Barinov, S.M., Rau, J.V., Teghil, R., Latini, A., “Calcium phosphate and fluorinated calcium phosphate coatings on titanium deposited by Nd:YAG laser at a high fluence”, Biomaterials, Vol. 26, (2005), 805–812.
29. Pei, X., Wang, J., Wan, Q., Kang, L., Xiao, M., Bao, H., “Functionally graded carbon nanotubes/hydroxyapatite composite coating by laser cladding”, Surface Coating Technology, Vol. 205, (2011), 4380–4387.
30. Oyane,A., Sakamaki, I., Shimizu, Y., Kawaguchi, K., Koshizaki, N., “Liquid-phase laser process for simple and areaspecific
calcium phosphate coating”, Journal of Biomedical Materials Research Part A, Vol. 100, (2012), 2573–2580.
31. Musaev, O.R., Dusevich, V., Wieliczka, D.M., Wrobel, J.M., and Kruger, M.B., “Nanoparticle fabrication of hydroxyapatite by laser ablation in water”, Journal of Applied Physics, Vol. 104, (2008), 084316-084321.
32. Guo, W., and Liu, B., “Liquid-phase pulsed laser ablation and electrophoretic deposition for chalcopyrite thin-film solar cell application”, ACS Appliled Materials Interfaces, Vol. 4, (2012), 7036−7042.
33. Qian, W., Murakami, M., Ichikawa, Y., and Che, Y., “Highly efficient and controllable pegylation of gold nanoparticles prepared by femtosecond laser ablation in water”, Journal of Physical Chemistry C, Vol. 115, (2011), 23293–23298.
34. Mhin, S.W., Ryu, J.H., Kim, K.M., Park, G.S., Ryu, H.W., Shim, K.B., Sasaki, T., Koshizaki, N., “Simple synthetic route for hydroxyapatite colloidal nanoparticles via a Nd:YAG laser ablation in liquid medium”, Applied Physics A, Vol. 96, (2009), 435–440.
35. Tamura, M., Endo, K., Maida, T., Ohno, H., “Hydroxyapatite film coating by thermally induced liquid phase deposition method for titanium implants”, Dental Materials Journal, Vol. 25, (2006), 32-38.
36. Safronova, T.V., Shiryaev, M.A., Putlyaev, V.I., Murashov, V.A., and Protsenko, P.V., “Ceramics based on hydroxyapatite synthesized from calcium chloride and potassium hydrophosphate”, Glass Ceramics, Vol. 66, (2009), 66-69.
37. Kokubo, T., Takadama, H., “How useful is SBF in predicting in vivo bone bioactivity?”, Biomaterial, Vol. 27, (2006) 2907- 2915.
38. Fernandez-Pradas, J.M., Sardin, G., Cleries, L., Serra, P., Ferrater, C., Morenza, J.L., “Deposition of hydroxyapatite thin films by excimer laser ablation”, Thin Solid Films, Vol. 317, (1998), 393-396.
39. Eslami, H., Solati-Hashjin, M., Tahriri, M., “Synthesis and characterization of hydroxyapatite nanocrystals via chemical precipitation technique”, Iranian Journal Of Pharmaceutical Sciences, Vol. 4, (2008), 127-134.
40. Chien, C.S., Han, T.J., Hong, T.F., Kuo, T.Y., and Liao, T.Y., “Effects of Different hydroxyapatite binders on morphology, Ca/P ratio and hardness of Nd-YAG laser clad coatings”, Materials Transactions, Vol. 50, (2009), 2852-2857.
41. Chien, C., Liao, T., Hong, T., Kuo, T., Chang, C., Yeh, M., Lee, T., “Surface microstructure and bioactivity of hydroxyapatite and fluorapatite coatings deposited on Ti-6Al- 4V substrates using Nd-YAG laser”, Journal Of Medical And Biological Engineering, Vol. 34, (2014), 109-115.
42. Bagratashvili, V.N., Antonov, E.N., Sobol, E.N., Popov, V.K., Howdle, S.M., “Macroparticle distribution and chemical composition of laser deposited apatite coatings”, Applied Physics Letters, Vol. 66, (1995), 2451-2453.
43. Johnson, S., “Pulsed laser deposition of hydroxyapatite thin films”, Master Thesis, Georgia Institiute of Technology, (2005).
44. Kokubo, T., and Yamaguchi, S., “Novel bioactive titanate layers formed on Ti metal and its alloys by chemical treatments”, Materials, Vol. 3, (2010), 48-63.
45. Hsu, H., Wu, S., Hsu, S., Chuang, S., Ho, W., “Surface modification of commercially pure Ti treated with aqueous NaOH treatment and ethyl alcohol aging”, Journal Of Medical And Biological Engineering, Vol. 33, (2013), 331-336.
46. Yamaguchi, S., Takadama, H., Matsushita, T., Nakamura, T., Kokubo, T., “Preparation of bioactive Ti-15Zr-4Nb-4Ta alloy from HCl and heat treatments after NaOH treatment”, Journal of Biomedical Materials Research A, Vol. 97, (2011), 135- 144.
47. Teixeira, R.L.P., Durães de Godoy, G.C., de Magalhães Pereira, M., “Calcium phosphate formation on alkali-treated titanium alloy and stainless steel”, Materials Research, Vol. 7, (2004), 299-303.
48. Ho, W., Lai, C., Hsu, H., Wu, S., “Surface modification of a Ti–7.5Mo alloy using NaOH treatment and Bioglass coating”, Journal of Materials Science; Materials in Medcine, Vol. 21, (2010), 1479–1488.
49. Abou Shahba, R.M., Ahmed, A.S.I., El-Shenawy, A.E.S., “Effect of natural products on the corrosion of titanium and its alloy in NaOH solutions”, International Journal of cancer, Vol. 4, (2012), 30-38.