Evaluation of Corrosion and Antimicrobial Properties of Polycaprolactone-Hydroxyapatite/ Tetracycline Coating on Magnesium Alloy for Orthopedic Applications
محورهای موضوعی : Bio Materials
Seyed Mostafa Hosseini
1
,
Hamid Ghayour
2
,
Saeid Jabbarzare
3
,
Masoud Kasiri-Asgarani
4
,
Reza Ebrahimi-Kahrizsangi
5
,
Mehdi Omidi
6
,
Hamid Reza Bakhsheshi Rad
7
1 - Department of Materials Engineering, Na.C., Islamic Azad University, Najafabad, Iran
2 - Department of Materials Engineering, Na.C., Islamic Azad University, Najafabad, Iran
3 - Department of Materials Engineering, Na.C., Islamic Azad University, Najafabad, Iran
4 - Department of Materials Engineering, Na.C., Islamic Azad University, Najafabad, Iran
5 - Department of Materials Engineering, Na.C., Islamic Azad University, Najafabad, Iran
6 - Department of Materials Engineering, Na.C., Islamic Azad University, Najafabad, Iran
7 - Department of Materials Engineering, Na.C., Islamic Azad University, Najafabad, Iran
کلید واژه: Magnesium, composite coating, polycaprolactone, hydroxyapatite, corrosion properties,
چکیده مقاله :
Magnesium alloys have attracted special attention in the field of orthopedic implants due to their mechanical properties close to natural bone, high biocompatibility, and biodegradability that eliminates the need for secondary surgery for implant removal. However, the rapid corrosion and high degradation rate of magnesium remain one of the main challenges in its clinical applications. One effective solution to overcome this problem is to modify the surface of magnesium alloys using biocompatible coatings Therefore, in this study, the modification of the magnesium surface by polycaprolactone (PCL) containing different percentages of hydroxyapatite (HA) and tetracycline (TC) was investigated in order to improve corrosion resistance and antibacterial properties. The results showed that the PCL-HA/TC composite coating has a dense structure with great bonding to the substrate. However, the contact angle of the coated samples was significantly reduced to 81° by adding HA and TC, which has an effective effect on the bioactivity of the coated Mg alloy. Electrochemical studies indicated that the corrosion resistance of Mg alloy was significantly increased after the application of PCL coatings containing HA and TC. The polarization test also confirmed this finding and showed that the coated samples had higher corrosion resistance than the uncoated sample. In addition, antibacterial tests showed that the PCL-HA/TC coating with a higher percentage of TC exhibited stronger antimicrobial activity, which confirms the high efficiency of this coating in providing simultaneous corrosion protection and disinfection.
Magnesium alloys have attracted special attention in the field of orthopedic implants due to their mechanical properties close to natural bone, high biocompatibility, and biodegradability that eliminates the need for secondary surgery for implant removal. However, the rapid corrosion and high degradation rate of magnesium remain one of the main challenges in its clinical applications. One effective solution to overcome this problem is to modify the surface of magnesium alloys using biocompatible coatings Therefore, in this study, the modification of the magnesium surface by polycaprolactone (PCL) containing different percentages of hydroxyapatite (HA) and tetracycline (TC) was investigated in order to improve corrosion resistance and antibacterial properties. The results showed that the PCL-HA/TC composite coating has a dense structure with great bonding to the substrate. However, the contact angle of the coated samples was significantly reduced to 81° by adding HA and TC, which has an effective effect on the bioactivity of the coated Mg alloy. Electrochemical studies indicated that the corrosion resistance of Mg alloy was significantly increased after the application of PCL coatings containing HA and TC. The polarization test also confirmed this finding and showed that the coated samples had higher corrosion resistance than the uncoated sample. In addition, antibacterial tests showed that the PCL-HA/TC coating with a higher percentage of TC exhibited stronger antimicrobial activity, which confirms the high efficiency of this coating in providing simultaneous corrosion protection and disinfection.
[1] C. Liu, Q. Jiang, D. Han, Y. Chen, W. Liu, Y. Pei, J. Duan, B. Hou, Preparation of multifunctional composite coating on magnesium alloys with corrosion resistance, conductivity and antibacterial properties, Journal of Magnesium and Alloys (2025).
[2] X. Xue, C. Liang, D. Wang, F. Peng, The research progress of self-healing coatings for magnesium/magnesium alloy, Journal of Alloys and Compounds 960 (2023) 170710.
[3] Z.-Q. Zhang, B.-Z. Li, P.-D. Tong, S.-K. Guan, L. Wang, Z.-H. Qiu, C.-G. Lin, R.-C. Zeng, Degradation and biocompatibility of one-step electrodeposited magnesium thioctic acid/magnesium hydroxide hybrid coatings on ZE21B alloys for cardiovascular stents, Journal of Magnesium and Alloys 12(1) (2024) 120–138.
[4] N. Singh, U. Batra, K. Kumar, A. Mahapatro, Investigating TiO2–HA–PCL hybrid coating as an efficient corrosion resistant barrier of ZM21 Mg alloy, Journal of Magnesium and Alloys 9(2) (2021) 627–646.
[5] H.R. Bakhsheshi-Rad, M.R. Abdul-Kadir, M.H. Idris, S. Farahany, Relationship between the corrosion behavior and the thermal characteristics and microstructure of Mg–0.5Ca–xZn alloys, Corrosion Science 64 (2012) 184–197.
[6] A. Saberi, H.R. Bakhsheshi-Rad, E. Karamian, M. Kasiri-Asgarani, H. Ghomi, A study on the corrosion behavior and biological properties of polycaprolactone/ bredigite composite coating on biodegradable Mg-Zn-Ca-GNP nanocomposite, Progress in Organic Coatings 147 (2020) 105822.
[7] A. Abdal-hay, T. Amna, J.K. Lim, Biocorrosion and osteoconductivity of PCL/nHAp composite porous film-based coating of magnesium alloy, Solid State Sciences 18 (2013) 131–140.
[8] H. Khatun, M. Rahman, S. Mahmud, M.O. Ali, M. Akter, Current advancements of hybrid coating on Mg alloys for medical applications, Results in Engineering 18 (2023) 101162.
[9] L.-Y. Li, L.-Y. Cui, R.-C. Zeng, S.-Q. Li, X.-B. Chen, Y. Zheng, M.B. Kannan, Advances in functionalized polymer coatings on biodegradable magnesium alloys – A review, Acta Biomaterialia 79 (2018) 23–36.
[10] N. U, R.K. L, E. Parfenov, R. N, Bioceramic (HA/BG) particles incorporated PCL-PEO hybrid coated ZM21 magnesium alloy for temporary orthopaedic implant application, Ceramics International (2025).
[11] E. Dayaghi, H.R. Bakhsheshi-Rad, E. Hamzah, A. Akhavan-Farid, A.F. Ismail, M. Aziz, E. Abdolahi, Magnesium-zinc scaffold loaded with tetracycline for tissue engineering application: In vitro cell biology and antibacterial activity assessment, Materials Science and Engineering: C 102 (2019) 53–65.
[12] H.M. Wong, K.W.K. Yeung, K.O. Lam, V. Tam, P.K. Chu, K.D.K. Luk, K.M.C. Cheung, A biodegradable polymer-based coating to control the performance of magnesium alloy orthopaedic implants, Biomaterials 31(8) (2010) 2084–2096.
[13] A.-M. Zhang, P. Lenin, R.-C. Zeng, M.B. Kannan, Advances in hydroxyapatite coatings on biodegradable magnesium and its alloys, Journal of Magnesium and Alloys 10(5) (2022) 1154–1170.
[14] Z.-Z. Yin, W.-C. Qi, R.-C. Zeng, X.-B. Chen, C.-D. Gu, S.-K. Guan, Y.-F. Zheng, Advances in coatings on biodegradable magnesium alloys, Journal of Magnesium and Alloys 8(1) (2020) 42–65.
[15] N. Singh, U. Batra, K. Kumar, N. Ahuja, A. Mahapatro, Progress in bioactive surface coatings on biodegradable Mg alloys: A critical review towards clinical translation, Bioactive Materials 19 (2023) 717–757.
[16] S.V. Dorozhkin, Calcium orthophosphate coatings on magnesium and its biodegradable alloys, Acta Biomaterialia 10(7) (2014) 2919–2934.
[17] M. Shamsi, M. Sedighi, A. Bagheri, Surface modification of biodegradable Mg/HA composite by electrospinning of PCL/HA fibers coating: Mechanical properties, corrosion, and biocompatibility, Transactions of Nonferrous Metals Society of China 34(5) (2024) 1470–1486.
[18] N.S. Grewal, U. Batra, K. Kumar, A. Mahapatro, Novel PA encapsulated PCL hybrid coating for corrosion inhibition of biodegradable Mg alloys: A triple triggered self-healing response for synergistic multiple protection, Journal of Magnesium and Alloys 11(4) (2023) 1440–1460.
[19] M. Asaduzzaman Chowdhury, M.D. Helal Hossain, N. Hossain, Z. Hossen, M. Arefin Kowser, M. Masud Rana, Advances in coatings on Mg alloys and their anti-microbial activity for implant applications, Arabian Journal of Chemistry 15(11) (2022) 104214.
[20] M. Tian, Z. Lin, W. Tang, W. Wu, L. Wang, J. Zhang, Electrophoretic deposition of tetracycline loaded bioactive glasses/chitosan as antibacterial and bioactive composite coatings on magnesium alloys, Progress in Organic Coatings 184 (2023) 107841.
[21] F. Long, L.-J. Qi, H.-F. Zhang, L. Zhao, M.-N. Zhang, Z.-Q. Zhang, J.-A. Li, S.-K. Guan, Advances and prospects in drug-like coatings on Mg alloy cardiovascular stents: A review, Journal of Magnesium and Alloys (2025).
[22] Z. Chunyan, C. Lan, L. Jiajia, S. Dongwei, Z. Jun, L. Huinan, In vitro evaluation of degradation, cytocompatibility and antibacterial property of polycaprolactone/hydroxyapatite composite coating on bioresorbable magnesium alloy, Journal of Magnesium and Alloys 10(8) (2022) 2252–2265.
[23] H.R.B. Rad, M.H. Idris, M.R.A. Kadir, S. Farahany, Microstructure analysis and corrosion behavior of biodegradable Mg–Ca implant alloys, Materials & Design 33 (2012) 88–97.
[24] B. Barai, K. Boorgula, H. Begam, S. Sarkar, A. Barui, S. Kundu, B. Oraon, T. Mandal, Multiphysics simulation and experimental investigation of HA and Zn-doped HA coatings on magnesium alloys for resorbable implant applications, Materials Today Communications 42 (2025) 111241.
[25] N. Singh, U. Batra, K. Kumar, A. Mahapatro, Evaluation of corrosion resistance, mechanical integrity loss and biocompatibility of PCL/HA/TiO2 hybrid coated biodegradable ZM21 Mg alloy, Journal of Magnesium and Alloys 10(11) (2022) 3179–3204.
[26] H.R. Bakhsheshi-Rad, M.H. Idris, M.R. Abdul-Kadir, A. Ourdjini, M. Medraj, M. Daroonparvar, E. Hamzah, Mechanical and bio-corrosion properties of quaternary Mg–Ca–Mn–Zn alloys compared with binary Mg–Ca alloys, Materials & Design 53 (2014) 283–292.
[27] J. Zhou, Y. Yang, R. Detsch, A.R. Boccaccini, S. Virtanen, Iron surface functionalization system - Iron oxide nanostructured arrays with polycaprolactone coatings: Biodegradation, cytocompatibility, and drug release behavior, Applied Surface Science 492 (2019) 669–682.
[28] A. Fattah-alhosseini, M. Molaei, M. Nouri, K. Babaei, Antibacterial activity of bioceramic coatings on Mg and its alloys created by plasma electrolytic oxidation (PEO): A review, Journal of Magnesium and Alloys 10(1) (2022) 81–96.
