Abstract
In this work, a magnesium phytic acid/hydroxyapatite composite coating was successfully prepared on AZ31 magnesium alloy substrate by chemical conversion deposition technology with the aim of improving its corrosion resistance and bioactivity. The influence of hydroxyapatite (HA) content on the microstructure and corrosion resistance of the coatings was investigated. The results showed that with the increase of HA content in phytic acid solution, the cracks on the surface of the coatings gradually reduced, which subsequently improved the corrosion resistance of these coated magnesium alloy. Electrochemical measurements in simulated body fluid (SBF) revealed that the composite coating with 45 wt.% HA addition exhibited superior surface integrity and significantly improved corrosion resistance compared with the single phytic acid conversion coating. The results of the immersion test in SBF showed that the composite coating could provide more effective protection for magnesium alloy substrate than that of the single phytic acid coating and showed good bioactivity.
Graphical Abstract
Magnesium phytic acid/hydroxyapatite composite, with the desired bioactivity, can be synthesized through chemical conversion deposition technology as protective coatings for surface modification of the biodegradable magnesium alloy implants. The design idea of the new type of biomaterial is belong to the concept of “third generation biomaterial”. Corrosion behavior and bioactivity of coated magnesium alloy are the key issues during implantation. In this study, preparation and corrosion behavior of magnesium phytic acid/hydroxyapatite composite coatings on magnesium alloy were studied.
The basic findings and significance of this paper are as follows:
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1.
A novel environmentally friendly, homogenous and crack-free magnesium phytic acid/hydroxyapatite composite coating was fabricated on AZ31 magnesium alloy via chemical conversion deposition technology with the aim of enhancing its corrosion resistance and bioactivity. The chemical conversion coatings, which are formed through the reaction between the substrate and the environment, have attracted increasing attention owing to the relative low treatment temperature, favorable bonding to substrate and simple implementation process.
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2.
With the increasing of hydroxyapatite (HA) content, the crack width in the composite coatings and the thickness of the coatings exhibit obviously decreased. The reason is probably that when adding HA into the phytic acid solution, the amount of active hydroxyl groups in the phytic acid are reduced via forming the coordination bond between P–OH groups from phytic acid and P–OH groups from the surface of HA, thus decreasing the coating thickness and hydrogen formation, as well as avoiding coating cracking.
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3.
By adjusting the HA content to 45 wt.%, a dense and relatively smooth composite coating with ~1.4 μm thickness is obtained on magnesium alloy, and exhibits high corrosion resistance and good bioactivity when compared with the single phytic acid conversion coating.
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References
Carboneras M, García-Alonso MC, Escudero ML. Biodegradation kinetics of modified magnesium-based materials in cell culture medium. Corros Sci. 2011;53:1433–9.
Witte F, Kaese V, Haferkamp H, Switzer E, Meyer-Lindenberg A, Wirth CJ, Windhagen H. In vivo corrosion of four magnesium alloys and the associated bone response. Biomaterials. 2005;26:3557–63.
Li LC, Gao JC, Wang Y. Evaluation of cyto-toxicity and corrosion behavior of alkali-heat-treated magnesium in simulated body fluid. Surf Coat Technol. 2004;185:92–8.
Zomorodian A, Brusciotti F, Fernandes A, Carmezim MJ, Moura e Silva T. Fernandes JCS. Anti-corrosion performance of a new silane coating for corrosion protection of AZ31 magnesium alloy in Hank’s solution. Surf Coat Technol. 2012;206:4368–75.
Staiger MP, Pietak AM, Huadmai J, Dias G. Magnesium and its alloys as orthopedic biomaterials: a review. Biomaterials. 2006;27:1728–34.
Chen X, Li G, Lian J, Jiang Q. Study of the formation and growth of tannic acid based conversion coating on AZ91D magnesium alloy. Surf Coat Technol. 2009;204:736–47.
Huang K, Cai S, Xu GH, Ye XY, Dou Y, Ren MG, Wang XX. Preparation and characterization of mesoporous 45S5 bioactive glass-ceramic coatings on magnesium alloy for corrosion protection. J Alloy Compd. 2013;580:290–7.
Zhang RF, Zhang SF, Duo SW. Influence of phytic acid concentration on coating properties obtained by MAO treatment on magnesium alloys. Appl Surf Sci. 2009;255:7893–7.
Meng EC, Guan SK, Wang HX, Wang LG, Zhu SJ, Hu JH, Ren CX, Gao JH, Feng YS. Effect of electrodeposition modes on surface characteristics and corrosion properties of fluorine-doped hydroxyapatite coatings on Mg–Zn–Ca alloy. Appl Surf Sci. 2011;257:4811–6.
Zhang RY, Cai S, Xu GH, Zhao H, Li Y, Wang XX, Huang K, Ren MG, Wu XD. Crack self-healing of phytic acid conversion coating on AZ31 magnesium alloy by heat treatment and the corrosion resistance. Appl Surf Sci. 2014;313:896–904.
Crea F, Stefano CD, Milea D, Sammartano S. Formation and stability of phytate complexes in solution. Coordin Chem Rev. 2008;252:1108–20.
Torres J, Domínguez S, Cerdá MF, Obal G, Mederos A, Irvine RF, Díaz A, Kremer C. Solution behaviour of myo-inositol hexakisphosphate in the presence of multivalent cations. Prediction of a neutral pentamagnesium species under cytosolic/nuclear conditions. J Inorg Biochem. 2005;99:828–40.
Cui XF, Li QF, Li Y, Wang FH, Jin G, Ding MH. Microstructure and corrosion resistance of phytic acid conversion coatings for magnesium alloy. Appl Surf Sci. 2008;255:2098–103.
Cui XF, Li Y, Li QF, Jin G, Ding MH, Wang FH. Influence of phytic acid concentration on performance of phytic acid conversion coatings on the AZ91D magnesium alloy. Mater Chem Phys. 2008;111:503–7.
Liu JR, Guo YN, Huang WD. Study on the corrosion resistance of phytic acid conversion coating for magnesium alloys. Surf Coat Technol. 2006;201:1536–41.
Liu JR, Guo YN, Huang WD. Phytic acid conversion coatings of magnesium. Chin J Chem. 2010;28:639–46.
Tang S, Tian B, Guo YJ, Zhu ZA, Guo YP. Chitosan/carbonated hydroxyapatite composite coatings: fabrication, structure and biocompatibility. Surf Coat Technol. 2014;251:210–6.
Allo BA, Rizkalla AS, Mequanint K. Hydroxyapatite formation on sol-gel derived poly(ε-caprolactone)/bioactive glass hybrid biomaterials. ACS Appl Mater Interfaces. 2014;4:3148–56.
Li Y, Cai S, Xu GH, Shen SB, Zhang M, Zhang T, Sun XH. Synthesis and characterization of a phytic acid/mesoporous 45S5 bioglass composite coating on a magnesium alloy and degradation behavior. RSC Adv. 2015;5:25708–16.
Zhang M, Cai S, Shen SB, Xu GH, Li Y, Ling R, Wu XD. In-situ defect repairing in hydroxyapatite/phytic acid hybrid coatings on AZ31 magnesium alloy by hydrothermal treatment. J Alloys Compd. 2015;658:649–56.
Abdal-hay A, Barakat NAM, Lim JK. Hydroxyapatite-doped poly(lactic acid) porous film coating for enhanced bioactivity and corrosion behavior of AZ31 Mg alloy for orthopedic applications. Ceram Int. 2013;39:183–95.
ASTM Standard G31-72. Standard practice for laboratory immersion corrosion testing of metals. Philadelphia, PA: ASTM Standards; 2004.
Zhang XY, Li Q, Li LQ, Zhang P, Wang ZW, Chen FN. Fabrication of hydroxyapatite/stearic acid composite coating and corrosion behavior of coated magnesium alloy. Mater Lett. 2012;88:76–8.
Aissa A, Debbabi M, Gruselle M, Thouvenot R, Gredin P, Traksmaa R, Tõ nsuaadu K. Covalent modification of calcium hydroxyapatite surface by grafting phenyl phosphonate moieties. J Solid State Chem. 2007;180:2273–8.
D’Andrea SC, Fadeev AY. Covalent surface modification of calcium hydroxyapatite using n-alkyl- and n-fluoroalkylphosphonic acids. Langmuir. 2003;19:7904–10.
Dou Y, Cai S, Ye XY, Xu GH, Huang K, Wang XX, Ren MG. 45S5 bioactive glass–ceramic coated AZ31 magnesium alloy with improved corrosion resistance. Surf Coat Technol. 2013;228:154–61.
Ye XY, Cai S, Xu GH, Dou Y, Hu HT, Ye XJ, Zhao H, Sun XH. The influence of mesopores on the corrosion resistance of hydroxyapatite coated AZ31 Mg alloy. J Electrochem Soc. 2014;161:45–50.
Ren MG, Cai S, Liu TL, Huang K, Wang XX, Zhao H, Niu SX, Zhang RY, Wu XD. Calcium phosphate glass/MgF2 double layered composite coating for improving the corrosion resistance of magnesium alloy. J Alloys Compd. 2014;591:34–40.
Wang XX, Cai S, Liu TL, Ren MG, Huang K, Zhang RY, Zhao H. Fabrication and corrosion resistance of calcium phosphate glass-ceramic coated Mg alloy via a PEG assisted sol–gel method. Ceram Int. 2014;40:3389–98.
Jamesh M, Kumar S. Narayanan TSNS. Electrodeposition of hydroxyapatite coating on magnesium for biomedical applications. J Coating Tech Res. 2012;9:495–502.
Acknowledgements
Authors acknowledge the financial support by the Tianjin Natural Science Foundation (Grant No. 15JCYBJC47500) and National Nature Science Foundation of China (Grant No. 51572186, 51372166 and 81271954). The authors acknowledge Mr. Chang lin for their help in the experimental work via Tianjin – Hainan university innovation fund cooperation project (Grant No. 2015X-0002).
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Zhang, M., Cai, S., Zhang, F. et al. Preparation and corrosion resistance of magnesium phytic acid/hydroxyapatite composite coatings on biodegradable AZ31 magnesium alloy. J Mater Sci: Mater Med 28, 82 (2017). https://doi.org/10.1007/s10856-017-5876-9
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DOI: https://doi.org/10.1007/s10856-017-5876-9