Pulsed laser-deposited hopeite coatings on titanium alloy for orthopaedic implant applications: surface characterization, antibacterial and bioactivity studies

  • Ashish DasEmail author
  • Mukul Shukla
Technical Paper


Although titanium and its alloys hold a significant position as an implant material for orthopedic and dental applications, they exhibit limited osteogenic and protective performance. The present research aims to develop an alternate process route for deposition of hopeite coatings on Titanium Grade 5 alloy (Ti–6Al–4V), using the pulsed laser deposition (PLD) technique. SEM, AFM and XRD were used to characterize and ellipsometer and tensometer were used to test the thickness and adhesive strength of the deposited hopeite coatings. While the FACS technique was used to assess their antibacterial activity, the simulated body fluid immersion test was utilized to ascertain their bioactivity. Lastly surface wettability and corrosion resistance of the hopeite coatings were evaluated using contact angle goniometer and potentiostat/galvanostat potentiodynamic (model PARSTAT 2263, Princeton Applied Research, USA), respectively. The PLD technique resulted in the deposition of hopeite coatings with desired crystallinity, adhesive strength of (16.52 ± 1.8 MPa), bioactivity, hydrophobic surface (water contact angle = 135°), superior corrosion resistance (Rp = 34,138.68 Ω cm2) and average surface roughness of (7.43 nm), which is likely to promote better osseointegration. The promising biological characteristics obtained in this research confirmed that the PLD hopeite coatings could be potentially used in orthopaedic implant applications.


Coating Hopeite Pulsed laser deposition Ti–6Al–4V Implant 



The use of synthesis, testing and characterization facilities of the Centre for Interdisciplinary Research (CIR), Centre for Medical Diagnostic and Research (CMDR), Biotechnology and Applied Mechanics Departments, MNNIT, Allahabad are gratefully acknowledged. The authors also thank Dr Naresh Kumar, Mr. Aashish Jha, Mr. Alok Kumar Yadav for their valuable contribution in the successful conduction of the experiments. The authors would like to thank the Ministry of Human Resource Development, Government of India and the University of Johannesburg, South Africa, for providing financial support.


  1. 1.
    Yang WH, Xi XF, Si Y, Huang S, Wang JF, Cai KY (2014) Surface engineering of titanium alloy substrates with multilayered biomimetic hierarchical films to regulate the growth behaviors of osteoblasts. Acta Biomater 10:4525–4536CrossRefGoogle Scholar
  2. 2.
    Hallab NJ, Vermes C, Messina C, Roebuck KA, Glant TT, Jacobs JJ (2002) Concentration and composition dependent effects of metal ions on human MG-63 osteoblasts. J Biomed Mater Res 60:420–433CrossRefGoogle Scholar
  3. 3.
    Sun ZL, Wataha JC, Hanks CT (1997) Effects of metal ions on osteoblast like cell metabolism and differentiation. J Biomed Mater Res 34:29–37CrossRefGoogle Scholar
  4. 4.
    Thompson GJ, Puelo DA (1996) Ti–6Al–4V ion solution inhibition of osteogenic cell phenotype as a function of differentiation time course in vitro. Biomaterials 17:1949–1954CrossRefGoogle Scholar
  5. 5.
    Wang JY, Wicklund BH, Gustilo RB, Tsukayama DT (1997) Prosthetic metals interfere with the functions of human osteoblast cells in vitro. Clin Orthop Relat Res 339:216–226CrossRefGoogle Scholar
  6. 6.
    Mohammed MT, Khan ZA, Siddiquee AN (2012) Titanium and its alloys, the imperative materials for biomedical applications. In: ICRTET, pp 91–95Google Scholar
  7. 7.
    Yu J, Chu X, Cai Y, Tong P, Yao J (2014) Preparation and characterization of antimicrobial nano hydroxyapatite composites. Mater Sci Eng C 37:54–59CrossRefGoogle Scholar
  8. 8.
    Park JW, Park KB, Suh JY (2007) Effects of calcium ion incorporation on bone healing of Ti6Al4V alloy implants in rabbit tibiae. Biomaterials 28:3306–3313CrossRefGoogle Scholar
  9. 9.
    Sridhar TM, Arumugam TK, Rajeswari S, Subbaiyan M (1997) Electrochemical behaviour of hydroxyapatite-coated stainless steel implants. J Mater Sci Lett 16:1964–1966CrossRefGoogle Scholar
  10. 10.
    Yamaguchi M, Oishi H, Suketa Y (1987) Stimulatory effect of zinc on bone formation in tissue culture. J Mater Sci Lett 36:4007–4012Google Scholar
  11. 11.
    Eberle J, Schmidmayer S, Erben RG, Stangassinger M, Roth HP (1999) Skeletal effects of zinc deficiency in growing rats. J Trace Elem Med Biol 13:21–26CrossRefGoogle Scholar
  12. 12.
    Chen D, Waite LC, Pierce WM Jr (1999) In vitro effects of zinc on markers of bone formation. Biol Trace Elem Res 68:225–234CrossRefGoogle Scholar
  13. 13.
    Shibli SMA, Jayalekshmi AC (2008) Development of phosphate inter layered hydroxyapatite coating for stainless steel implants. Appl Surf Sci 254:4103–4110CrossRefGoogle Scholar
  14. 14.
    Herschke L, Rottstegge J, Lieberwirth I, Wegner G (2006) Zinc phosphate as versatile material for potential biomedical applications part 1. J Mater Sci Mater Med 17:81–94CrossRefGoogle Scholar
  15. 15.
    Nriagu JO (1973) Solubility equilibrium constant of α-hopeite. Geochim Cosmochim Acta 37:2357–2361CrossRefGoogle Scholar
  16. 16.
    Uo M, Sjoren G, Sundh A, Watari F, Bergman M, Lerner U (2003) Cytotoxicity and bonding property of dental ceramics. Int J Appl Glass Sci 19:487–492Google Scholar
  17. 17.
    Attar N, Tam LE, McComb D (2003) Mechanical and physical properties of contemporary dental luting agents. J Prosthet Dent 89:127–134CrossRefGoogle Scholar
  18. 18.
    Horiuchi S, Asaoka K, Tanaka E (2009) Development of a novel cement by conversion of hopeite in set zinc phosphate cement into biocompatible apatite. Biomed Mater Eng 19:121–131Google Scholar
  19. 19.
    Lin FH, Hsu YS, Lin SH, Sun JS (2002) The effect of Ca/P concentration and temperature of simulated body fluid on the growth of hydroxyapatite coating on alkali-treated 316L stainless steel. Biomaterials 23:4029–4038CrossRefGoogle Scholar
  20. 20.
    Kokubo T, Ito S, Sakka S, Yamamuro T (1986) Formation of a high strength bioactive glass–ceramic in the system MgO–CaO–SiO2–P2O5. J Mater Sci 21:536–540CrossRefGoogle Scholar
  21. 21.
    Kokubo T, Hayashi T, Sakka S, Kitsugi T, Yamamuro T (1987) Bonding between bioactive glasses, glass-ceramics or ceramics in simulated body fluid. yogyo-kyokai-hi 95:785–791CrossRefGoogle Scholar
  22. 22.
    Kokubo T, Kushitani H, Sakka S, Kitsugi T, Yamamuro T (1990) Solutions able to reproduce in vivo surface-structure changes in bioactive glass–ceramics A-W3. J Biomed Mater Res 24:721–734CrossRefGoogle Scholar
  23. 23.
    Kokubo T (1990) Surface chemistry of bioactive glass–ceramics. J Non Cryst Solids 120:138–151CrossRefGoogle Scholar
  24. 24.
    Aza PND, Guitian F, Aza SD (1994) Bioactivity of wollastonite ceramics: in vitro evaluation. Scr Metall Mater 31:1001–1005CrossRefGoogle Scholar
  25. 25.
    Liu DM (1994) Bioactive glass–ceramic: formation, characterization and bioactivity. Mater Chem Phys 36:294–303CrossRefGoogle Scholar
  26. 26.
    De Aza PN, Luklinska ZB, Anseau MR, Guitian F, De Aza S (1999) Bioactivity of pseudowollastonite in human saliva. J Dent 27:107–113CrossRefGoogle Scholar
  27. 27.
    De Aza PN, Luklinska Z (2003) Effect of the glass–ceramic microstructure on its in vitro bioactivity. J Mat Sci Mater Med 14:891–898CrossRefGoogle Scholar
  28. 28.
    De Aza PN, Luklinska ZB, Anseau MR (2005) Bioactivity of diopside ceramic in human parotid saliva. J Biomed Mater Res 73B:54–60CrossRefGoogle Scholar
  29. 29.
    Alemany MI, Velasquez P, de la Casa-Lillo MA, De Aza PN (2005) Effect of materials processing methods on the in vitro bioactivity of wollastonite glass–ceramic materials. J Non Cryst Solids 351:1716–1726CrossRefGoogle Scholar
  30. 30.
    Khan AN, Lu J (2007) Thermal cyclic behavior of air plasma sprayed thermal barrier coatings sprayed on stainless steel substrates. Surf Coat Technol 201:4653–4658CrossRefGoogle Scholar
  31. 31.
    Oskuie AA, Afshar A, Hasannejad H (2010) Effect of current density on DC electrochemical phosphating of stainless steel 316. Surf Coat Technol 205:2302–2306CrossRefGoogle Scholar
  32. 32.
    Valanezhad A, Tsuru K, Maruta M, Kawachi G, Matsuya S, Ishikawa K (2010) Zinc phosphate coating on 316L-type stainless steel using hydrothermal treatment. Surf Coat Technol 205:2538–2541CrossRefGoogle Scholar
  33. 33.
    Foerster CE, Serbena FC, da Silva SLR, Lepienski CM, Siqueira CJM, Ueda M (2007) Mechanical and tribological properties of AISI 304 stainless steel nitrided by glow discharge compared to ion implantation and plasma immersion ion implantation. Nucl Phys B 257:732–736Google Scholar
  34. 34.
    Tlotleng M, Akinlabi E, Shukla M, Pityana S (2014) Microstructures, hardness and bioactivity of hydroxyapatite coatings deposited by direct laser melting process. Mater Sci Eng C 43:189–198CrossRefGoogle Scholar
  35. 35.
    Garcia SFJ, Mayor MB, Arias JL, Pou J, Leon B, Perez AM (1997) Hydroxyapatite coatings: a comparative study between plasma-spray and pulsed laser deposition techniques. J Mater Sci Mater Med 8:861–865CrossRefGoogle Scholar
  36. 36.
    Bao Q, Chen C, Wang D, Ji Q, Lei T (2005) Pulsed laser deposition and its current research status in preparing hydroxyapatite thin films. Appl Surf Sci 252:1538–1544CrossRefGoogle Scholar
  37. 37.
    Bigi A, Bracci B, Cuisinier F, Elkaim R, Fini M, Mayer I, Mihailescu IN, Socol G, Sturba L, Torricelli P (2005) Human osteoblast response to pulsed laser deposited calcium phosphate coatings. Biomaterials 26:2381–2389CrossRefGoogle Scholar
  38. 38.
    Fernandez PJM, Garcia CMV, Cleries L, Sardin G, Morenza JL (2002) Influence of the interface layer on the adhesion of pulsed laser deposited hydroxyapatite coatings on titanium alloy. Appl Surf Sci 195:31–37CrossRefGoogle Scholar
  39. 39.
    Zeng H, Lacefield WR (2000) XPS, EDX and FTIR analysis of pulsed laser deposited calcium phosphate bioceramic coatings: the effects of various process parameters. Biomaterials 21:23–30CrossRefGoogle Scholar
  40. 40.
    Rajesh P, Muraleedharan CV, Komath M, Varma H (2011) Pulsed laser deposition of hydroxyapatite on titanium substrate with titania interlayer. J Mater Sci Mater Med 22:497–505CrossRefGoogle Scholar
  41. 41.
    Won YJ, Ki H (2013) Fabricating functionally graded films with designed gradient profiles using pulsed laser deposition. J Appl Phys 113:174910-1–174910-9Google Scholar
  42. 42.
    Tanaskovic D, Jokic B, Socol G, Popescu A, Mihailescu IN, Petrovic R, Janackovic D (2007) Synthesis of functionally graded bioactive glass-apatite multistructures on Ti substrates by pulsed laser deposition. App Surf Sci 254:1279–1282CrossRefGoogle Scholar
  43. 43.
    Rusop M, Uma K, Soga T, Jimbo T (2007) Structural properties of pulsed laser deposited zinc oxide thin films annealed at various temperatures. Surf Eng 23:230–233CrossRefGoogle Scholar
  44. 44.
    Kuppusami P, Raghunathan VS (2006) Status of pulsed laser deposition: challenges and opportunities. Surf Eng 22:81–83CrossRefGoogle Scholar
  45. 45.
    Khandelwal H, Singh G, Agrawal K, Prakash S, Agarwal RD (2013) Characterization of hydroxyapatite coating by pulse laser deposition technique on stainless steel 316 L by varying laser energy. Appl Surf Sci 265:30–35CrossRefGoogle Scholar
  46. 46.
    Zeng H, Lacefield WR, Mirov S (2000) Structural and morphological study of pulsed laser deposited calcium phosphate bioceramic coatings: Influence of deposition conditions, laser parameters, and target properties. J Biomed Mater Res 50:248–258CrossRefGoogle Scholar
  47. 47.
    Das A, Shukla M (2015) Surface morphology and adhesion studies of pulsed laser deposited hydroxyapatite thin film coatings on SS254 stainless steel. In: 24th DAE BRNS national laser symposium (NLS-24)Google Scholar
  48. 48.
    Das A, Shukla M (2016) Surface morphology, bioactivity, and antibacterial studies of pulsed laser deposited hydroxyapatite coatings on stainless steel 254 for orthopedic implant applications. J Mater Des Appl. CrossRefGoogle Scholar
  49. 49.
    Constantino ME, Campillo B, Staia MH, Serna S, Juarez-Islas J, Sudarshan TS (2006) Pulsed electrode deposition of super hard coatings on steel substrates: microstructural and chemical study. Surf Eng 22:212–218CrossRefGoogle Scholar
  50. 50.
    Wolkowicz R (2013) Fluorescence-activated cell sorting. In: Maloy S (ed) Brenner’s encyclopedia of genetics, 2nd edn. Academic Press, London, pp 80–82CrossRefGoogle Scholar
  51. 51.
    Saritha K, Rajesh A, Manjulatha K, Setty OH, Yenugu S (2015) Mechanism of antibacterial action of the alcoholic extracts of Hemidesmus indicus (L.) R. Br. exSchult, Leucas aspera (Wild.), Plumbago zeylanica L., and Tridax procumbens (L.) R. Br. ex Schult. Front Microbiol 6:577CrossRefGoogle Scholar
  52. 52.
    Das A, Shukla M (2017) Surface morphology and in vitro bioactivity of biocompatible hydroxyapatite coatings on medical grade S31254 steel by RF magnetron sputtering deposition. Trans IMF 95:276–281CrossRefGoogle Scholar
  53. 53.
    Das A, Shukla M (2017) Hydroxyapatite coatings on high nitrogen stainless steel by laser rapid manufacturing. JOM 69:2292–2296CrossRefGoogle Scholar
  54. 54.
    Yi W, Sun X, Niu D, Hu X (2014) In vitro bioactivity of 3D Ti-mesh with bioceramic coatings in simulated body fluid. J Asian Ceram Soc 2:210–214CrossRefGoogle Scholar
  55. 55.
    Kokubo T, Takadama H (2006) How useful is SBF in predicting in vivo bone bioactivity? Biomaterials 27:2907–2915CrossRefGoogle Scholar
  56. 56.
    Kassing R, Petkov P, Kulisch W, Popov C (2006) Functional properties of nanostructured materials, vol 223. Series II: mathematics, physics and chemistry. Springer, Berlin, pp 183–196Google Scholar
  57. 57.
    Brunette DM, Tengvall P, Textor M, Thomsen P (2001) Titanium in medicine. Springer, BerlinCrossRefGoogle Scholar
  58. 58.
    Dinda GP, Shin J, Mazumder J (2009) Pulse laser deposition of hydroxyapatite thin coatings on Ti–6Al–4V: effect of heat treatment on structure and properties. Acta Biomater 5:1821–1830CrossRefGoogle Scholar
  59. 59.
    Rad AT, Hashjin MS, Osman NAA, Faghihi S (2014) Improved bio-physical performance of hydroxyapatite coatings obtained by electrophoretic deposition at dynamic voltage. Ceram Int 40:12681–12691CrossRefGoogle Scholar
  60. 60.
    Roy M, Balla VK, Bandyopadhyay A, Bose S (2010) Comparison of tantalum and hydroxyapatite coatings on titanium for applications in load bearing implants. Adv Eng Mater 12:B637–B641CrossRefGoogle Scholar
  61. 61.
    Bandyopadhyay A, Balla VK, Roy M, Bose S (2011) Laser surface modification of metallic biomaterials. JOM 63:94–99CrossRefGoogle Scholar
  62. 62.
    Balla VK, Bhat A, Bose S, Bandyopadhyay A (2012) Laser processed TiN reinforced Ti6Al4V composite coatings. J Mech Behav Biomed Mater 6C:9CrossRefGoogle Scholar
  63. 63.
    Zhang X, Xiao G, Jiao Y, Zhao X, Lu Y (2014) Facile preparation of hopeite coating on stainless steel by chemical conversion method. Surf Coat Technol 240:361–364CrossRefGoogle Scholar
  64. 64.
    Driver M (2012) Coatings for biomedical applications. Woodhead Publishing Limited, CambridgeCrossRefGoogle Scholar
  65. 65.
    Blind O, Klein LH, Dailey B, Jordan L (2005) Characterization of hydroxyapatite films obtained by pulsed-laser deposition on Ti and Ti–6AL–4V substrates. Dent Mater 21:1017–1024CrossRefGoogle Scholar
  66. 66.
    Anselme K, Bigerelle M, Noel B, Dufresne E, Judas D, Iost A, Hardouin P (2000) Qualitative and quantitative study of human osteoblast adhesion on materials with various surface roughnesses. J Biomed Mater Res 49:155–166CrossRefGoogle Scholar
  67. 67.
    Zhang X, Xiao G, Jiang C, Liu B, Li N, Zhu R, Lu Y (2015) Influence of process parameters on microstructure and corrosion properties of hopeite coating on stainless steel. Corros Sci 94:428–437CrossRefGoogle Scholar
  68. 68.
    Ge X, Leng Y, Bao C, Xu SL, Wang R, Ren F (2010) Antibacterial coatings of fluoridated hydroxyapatite for percutaneous implants. J Biomed Mater Res A 95:588–599CrossRefGoogle Scholar
  69. 69.
    Puckett SD, Taylor E, Raimondo T, Webster TJ (2010) The relationship between the nanostructure of titanium surfaces and bacterial attachment. Biomaterials 31:706–713CrossRefGoogle Scholar
  70. 70.
    Man HC, Chiu KY, Cheng FT, Wong KH (2009) Adhesion study of pulsed laser deposited hydroxyapatite coating on laser surface nitrided titanium. Thin Solid Films 517:5496–5501CrossRefGoogle Scholar
  71. 71.
    Neo M, Kotani S, Nakamura T, Yamamuro T, Ohtsuki C, Kokubo T, Bando YA (1992) A comparative study of ultrastructures of the interfaces between four kinds of surface-active ceramic and bone. J Biomed Mater Res 26:1419–1432CrossRefGoogle Scholar
  72. 72.
    Gu YW, Khor KA, Cheang P (2004) Bone-like apatite layer formation on hydroxyapatite prepared by spark plasma sintering (SPS). Biomaterials 25:4127–4134CrossRefGoogle Scholar
  73. 73.
    Jones FH (2001) Teeth and bones: applications of surface science to dental materials and related biomaterials. Surf Sci Rep 42:75–205CrossRefGoogle Scholar
  74. 74.
    Wu W, Zhuang H, Nancollas GH (1997) Heterogeneous nucleation of calcium phosphates on solid surfaces in aqueous solution. J Biomed Mater Res 35:93–99CrossRefGoogle Scholar
  75. 75.
    Hench LL (1998) Bioceramics. J Am Ceram Soc 81:1705–1728CrossRefGoogle Scholar
  76. 76.
    Hench LL, Day DE, Holand W, Rheinberger VM (2010) Glass and medicine. Int J Appl Glass Sci 1:104–117CrossRefGoogle Scholar
  77. 77.
    Chavan PN, Bahir MM, Mene RU, Mahabole MP, Khairnar RS (2010) Study of nanobiomaterial hydroxyapatite in simulated body fluid: formation and growth of apatite. Mater Sci Eng B 168:224–230CrossRefGoogle Scholar
  78. 78.
    Wang YX, Robertson JL, Spillman WB, Claus RO (2004) Effects of the chemical structure and the surface properties of polymeric biomaterials and their biocompatibility. Pharm Res 21:1362–1373CrossRefGoogle Scholar
  79. 79.
    Wang J, Pan CJ, Huang N, Sun H, Yang P, Leng XY, Chen JY, Wan GJ, Chu PK (2005) Surface characterization and blood compatibility of poly(ethylene terephthalate) modified by plasma surface grafting. Surf Coat Technol 196:307–311CrossRefGoogle Scholar
  80. 80.
    Higuchi A, Shirano K, Harashima M, Yoon BO, Hara M, Hattori M, Imamura K (2002) Chemically modified polysulfone hollow fibers with vinylpyrrolidone having improved blood compatibility. Biomaterials 23:2659–2666CrossRefGoogle Scholar
  81. 81.
    MacDonald DE, Deo N, Markovic B, Stranick M, Somasundaran P (2002) Adsorption and dissolution behavior of human plasma fibronectin on thermally and chemically modified titanium dioxide particles. Biomaterials 23:1269–1279CrossRefGoogle Scholar
  82. 82.
    Hess H, Vogel V (2001) Molecular shuttles based on motor proteins: active transport in synthetic environments. J Biotechnol 82:67–85Google Scholar
  83. 83.
    Prakash C, Kansal HK, Pabla BS, Puri S (2015) Processing and characterization of novel biomimetic nanoporous bioceramic surface on β-Ti implant by powder mixed electric discharge machining. J Mater Eng Perform 24:3622–3633CrossRefGoogle Scholar

Copyright information

© The Brazilian Society of Mechanical Sciences and Engineering 2019

Authors and Affiliations

  1. 1.Department of Mechanical EngineeringMNNITAllahabadIndia
  2. 2.Department of Manufacturing EngineeringNITJamshedpurIndia
  3. 3.School of Mechanical and Aerospace EngineeringQueen’s UniversityBelfastUK
  4. 4.Department of Mechanical Engineering TechnologyUniversity of JohannesburgJohannesburgSouth Africa

Personalised recommendations