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Corrosion-resistant fluoridated Ca–Mg–P composite coating on magnesium alloys prepared via hydrothermal assisted sol–gel process

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Abstract

In this work, corrosion-resistant fluoridated Ca–Mg–P composite coatings were prepared on magnesium alloys via a hydrothermal assisted sol–gel process. All these coatings derived from Coating Sols with different F− concentrations are composed of fluoridated hydroxyapatite, magnesium hydroxide, and dittmarite. When F− concentration of Coating Sol is 0.03 M, the coating exhibited uniform and dense surface, and its thickness reached 32 μm, thus possessing a high charge transfer resistance of 312 ± 12.69 kΩ cm2 in simulated body fluid (SBF). Immersion test in SBF showed that this coating could quickly induce the formation of the mineralized layer, implying relatively high bioactivity. After 49 days of immersion, the original composite coating and newly formed mineralized layer reached 60 μm in thickness, providing effective long-term protection for magnesium alloys. These attractive results indicate that this fluoridated Ca–Mg–P composite coating is a promising protective coating on biodegradable magnesium and magnesium alloy implants for orthopaedic applications.

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References

  1. M. Esmaily, J.E. Svensson, S. Fajardo, N. Birbilis, G.S. Frankel, S. Virtanen, R. Arrabal, S. Thomas, and L.G. Johansson: Fundamentals and advances in magnesium alloy corrosion. Prog. Mater. Sci. 89, 92–193 (2017).

    Article  CAS  Google Scholar 

  2. S.V. Dorozhkin: Calcium orthophosphate coatings on magnesium and its biodegradable alloys. Acta Biomater. 10, 2919–2934 (2014).

    Article  CAS  Google Scholar 

  3. Y. Xiong, X. Hu, and R. Song: Characteristics of CeO2/ZrO2-HA composite coating on ZK60 magnesium alloy. J. Mater. Res. 32, 1073–1082 (2017).

    Article  CAS  Google Scholar 

  4. S. Fooladi and S.R. Kiahosseini: Creation and investigation of chitin/HA double-layer coatings on AZ91 magnesium alloy by dipping method. J. Mater. Res. 32, 2532–2541 (2017).

    Article  CAS  Google Scholar 

  5. T.S. Lim, H.S. Ryu, and S.H. Hong: Plasma electrolytic oxidation/cerium conversion composite coatings for the improved corrosion protection of AZ31 Mg alloys. J. Electrochem. Soc. 160, 73–82 (2013).

    Article  Google Scholar 

  6. J. Qi, T. Hashimoto, J. Walton, X. Zhou, P. Skeldon, and G.E. Thompson: formation of a trivalent chromium conversion coating on AA2024-t351 alloy. J. Electrochem. Soc. 163, 25–35 (2016).

    Article  Google Scholar 

  7. S. Bauer, P. Schmuki, K. von der Mark, and J. Park: Engineering biocompatible implant surfaces part I: Materials and surfaces. Prog. Mater. Sci. 58, 261–326 (2013).

    Article  CAS  Google Scholar 

  8. K. Gregorczyk, and M. Knez: Hybrid nanomaterials through molecular and atomic layer deposition: Top down, bottom up, and in-between approaches to new materials. Prog. Mater. Sci. 75, 1–37 (2016).

    Article  CAS  Google Scholar 

  9. L. Chang, F. Cao, J. Cai, W. Liu, J. Zhang, and C. Cao: Formation and transformation of Mg(OH)2 in anodic coating using FTIR mapping. Electrochem. Commun. 11, 2245–2248 (2009).

    Article  CAS  Google Scholar 

  10. Y.J. Shi, J. Pei, J. Zhang, J.L. Niu, H. Zhang, S.R. Guo, Z.H. Li, and G.Y. Yuan: Enhanced corrosion resistance and cytocompatibility of biodegradable Mg alloys by introduction of Mg(OH)2 particles into poly(L-lactic acid) coating. Sci. Rep. 7, 1–10 (2017).

    Article  Google Scholar 

  11. H. Tang, F.J. Xu, W. Tao, and X. Jian: Fabrication and characterization of Mg(OH)2 films on AZ31 magnesium alloy by alkali treatment. Int. J. Electrochem. Sci., 12, 1377–1388 (2017).

    Article  CAS  Google Scholar 

  12. J. Jayaraj, S. Amruth Raj, A. Srinivasan, S. Ananthakumar, U.T.S. Pillai, N.G.K. Dhaipule, and U.K. Mudali: Composite magnesium phosphate coatings for improved corrosion resistance of magnesium AZ31 alloy. Corros. Sci. 113, 104–115 (2016).

    Article  CAS  Google Scholar 

  13. Q. Zhao, W. Mahmood, and Y. Zhu: Synthesis of dittmarite/Mg(OH)2 composite coating on AZ31 using hydrothermal treatment. Appl. Surf. Sci. 367, 249–258 (2016).

    Article  CAS  Google Scholar 

  14. T. Ishizaki, R. Kudo, T. Omi, K. Teshima, T. Sonoda, I. Shigematsu, and M. Sakamoto: Corrosion resistance of multilayered magnesium phosphate/magnesium hydroxide film formed on magnesium alloy using steam-curing assisted chemical conversion method. Electrochim. Acta 62, 19–29 (2012).

    Article  CAS  Google Scholar 

  15. S. Shen, S. Cai, Y. Li, R. Ling, F. Zhang, G. Xu, and F. Wang: Microwave aqueous synthesis of hydroxyapatite bilayer coating on magnesium alloy for orthopedic application. Chem. Eng. J. 309, 278–287 (2017).

    Article  CAS  Google Scholar 

  16. M. Manso, J.M. Martínez-Duart, M. Langlet, C. Jiménez, P. Herrero, and E. Millon: Aerosol–gel-derived microcrystalline hydroxyapatite coatings. J. Mater. Res. 17, 1482–1489 (2011).

    Article  Google Scholar 

  17. N. Yu, S. Cai, F. Wang, F. Zhang, R. Ling, Y. Li, Y. Jiang, and G. Xu: Microwave assisted deposition of strontium doped hydroxyapatite coating on AZ31 magnesium alloy with enhanced mineralization ability and corrosion resistance. Ceram. Int. 43, 2495–2503 (2017).

    Article  CAS  Google Scholar 

  18. S-H. Wang, C-W. Yang, and T-M. Lee: Evaluation of microstructural features and in vitro biocompatibility of hydrothermally coated fluorohydroxyapatite on AZ80 Mg alloy. Ind. Eng. Chem. Res. 55, 5207–5215 (2016).

    Article  CAS  Google Scholar 

  19. Y. Wang, S. Zhang, X. Zeng, L.L. Ma, W. Weng, W. Yan, and M. Qian: Osteoblastic cell response on fluoridated hydroxyapatite coatings. Acta Biomater. 3, 191–197 (2007).

    Article  CAS  Google Scholar 

  20. F.C.M. Driessens: Relation between apatite solubility and anti-cariogenic effect of fluoride. Nature 243, 420–421 (1973).

    Article  CAS  Google Scholar 

  21. L. Zhang, J. Pei, H. Wang, Y. Shi, J. Niu, F. Yuan, H. Huang, H. Zhang, and G. Yuan: Facile preparation of poly(lactic acid)/brushite bilayer coating on biodegradable magnesium alloys with multiple functionalities for orthopedic application. ACS Appl. Mater. Interfaces 9, 9437–9448 (2017).

    Article  CAS  Google Scholar 

  22. D.C. Romonţi, J. Iskra, M. Bele, I. Demetrescu, and I. Milošev: Elaboration and characterization of fluorohydroxyapatite and fluoroapatite sol–gel coatings on CoCrMo alloy. J. Alloys Compd. 665, 355–364 (2016).

    Article  Google Scholar 

  23. L. Gan and R. Pilliar: Calcium phosphate sol–gel-derived thin films on porous-surfaced implants for enhanced osteoconductivity. Part I: Synthesis and characterization. Biomaterials 25, 5303–5312 (2004).

    Article  CAS  Google Scholar 

  24. J. Zeng, C. Lin, J. Li, and K. Li: Low temperature preparation of barium titanate thin films by a novel sol–gel-hydrothermal method. Mater. Lett. 38, 112–115 (1999).

    Article  CAS  Google Scholar 

  25. N. Lu, Y. Zhao, H. Liu, Y. Guo, X. Yuan, H. Xu, H. Peng, and H. Qin: Design of polyoxometallate–titania composite film (H3PW12O40/TiO2) for the degradation of an aqueous dye Rhodamine B under the simulated sunlight irradiation. J. Hazard. Mater. 199–200, 1–8 (2012).

    Article  Google Scholar 

  26. H. Duan, Y.F. Zheng, Y.Z. Dong, X.G. Zhang, and Y.F. Sun: Pyrite (FeS2) films prepared via sol–gel hydrothermal method combined with electrophoretic deposition (EPD). Mater. Res. Bull. 39, 1861–1868 (2004).

    Article  CAS  Google Scholar 

  27. X. Zhang, S. Böhm, A.J. Bosch, E.P.M. van Westing, and J.H.W. de Wit: Influence of drying temperature on the corrosion performance of chromate coatings on galvanized steel. Mater. Corros. 55, 501–510 (2004).

    Article  CAS  Google Scholar 

  28. W. Lv, X. Lv, J. Xiang, Y. Zhang, S. Li, C. Bai, B. Song, and K. Han: A novel process to prepare high-titanium slag by carbothermic reduction of pre-oxidized ilmenite concentrate with the addition of Na2SO4. Int. J. Miner. Process. 167, 68–78 (2017).

    Article  CAS  Google Scholar 

  29. R.M. Bandeira, J. van Drunen, A.C. Garcia, and G. Tremiliosi-Filho: Influence of the thickness and roughness of polyaniline coatings on corrosion protection of AA7075 aluminum alloy. Electrochim. Acta 240, 215–224 (2017).

    Article  CAS  Google Scholar 

  30. K.S. Le Corre, E. Valsami-Jones, P. Hobbs, and S.A. Parsons: Impact of calcium on struvite crystal size, shape and purity. J. Cryst. Growth 283, 514–522 (2005).

    Article  Google Scholar 

  31. R. Manoj Kumar, K.K. Kuntal, S. Singh, P. Gupta, B. Bhushan, P. Gopinath, and D. Lahiri: Electrophoretic deposition of hydroxyapatite coating on Mg–3Zn alloy for orthopaedic application. Surf. Coat. Technol. 287, 82–92 (2016).

    Article  Google Scholar 

  32. H. Tang, T. Wu, and W. Hong: Corrosion behavior of the HA containing ceramic coated magnesium alloy in Hank’s solution. J. Alloys Compd. 698, 643–653 (2017).

    Article  CAS  Google Scholar 

  33. L. Abdoli, J. Huang, and H. Li: Electrochemical corrosion behaviors of aluminum-based marine coatings in the presence of Escherichia coli bacterial biofilm. Mater. Chem. Phys. 173, 62–69 (2016).

    Article  CAS  Google Scholar 

  34. V. Shinde and P.P. Patil: Evaluation of corrosion protection performance of poly(o-ethyl aniline) coated copper by electrochemical impedance spectroscopy. Mater. Sci. Eng., B 168, 142–150 (2010).

    Article  CAS  Google Scholar 

  35. G. Liu, S. Tang, D. Li, and J. Hu: Self-adjustment of calcium phosphate coating on micro-arc oxidized magnesium and its influence on the corrosion behaviour in simulated body fluids. Corros. Sci. 79, 206–214 (2014).

    Article  CAS  Google Scholar 

Download references

ACKNOWLEDGMENTS

The authors acknowledge the financial support by National Natural Science Foundation of China (Grant Nos. 51372166, 51572186, and 81271954), Tianjin Natural Science Foundation (Grant No. 15JCYBJC47500), Shanghai Committee of Science and Technology (Grant No. 16XD1424700), and the Shanghai Committee of Science and Technology, China (Grant No. 15411951000). The authors acknowledge Mr. Chang Lin for his help in the experimental work via Tianjin-Hainan university innovation fund cooperation project (Tianjin-Hainan university innovation fund cooperation project).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Key Laboratory for Advanced Ceramics and Machining Technology of Ministry of Education, Tianjin University, Tianjin, 300072, People’s Republic of China

    Yangyang Jiang, Shu Cai, Yue Li, Song Jiang, Yishu Lin, Shaoshuai Hua & Rui Ling

  2. Department of Orthopedic Surgery, Changzheng Hospital, Second Military Medical University, Shanghai, 200003, People’s Republic of China

    Lingjun Zhu & Guohua Xu

  3. Center for Electron Microscopy, Institute for New Energy Materials & Low-Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, 300384, People’s Republic of China

    Sibo Shen

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  1. Yangyang Jiang
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  2. Lingjun Zhu
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  3. Shu Cai
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Correspondence to Shu Cai, Sibo Shen or Guohua Xu.

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Jiang, Y., Zhu, L., Cai, S. et al. Corrosion-resistant fluoridated Ca–Mg–P composite coating on magnesium alloys prepared via hydrothermal assisted sol–gel process. Journal of Materials Research 33, 3793–3800 (2018). https://doi.org/10.1557/jmr.2018.270

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