Corrosion behavior of Ti-Cu coating on the surface of bone magnesium alloy

doi:10.3969/j.issn.2095-4344.2013.42.004

Abstract

Abstract:

BACKGROUND: Magnesium alloy as a fracture fixation material has mechanical properties similar to the bone, good biocompatibility and biodegradability, but its rapid degradation rate in body fluids becomes a clinical bottleneck. Therefore, the use of surface treatments to improve its corrosion resistance is important.
OBJECTIVE: To use magnetron sputtering technology and alkali heat treatment technology in the preparation of coating characterized as both corrosion resistance and biological activity.
METHODS: First, we prepared Mg-Zn-Mn alloy using the smelting technology, and prepared a dense coating on the alloy surface by the magnetron sputtering technique. Then, we processed the coating surface using an alkaline solution, and studied the corrosion behavior of the coating by use of simulated body fluid experiments. We speculated the biological activity of the coating by measuring the content of calcium and phosphorus from the surface products.
RESULTS AND CONCLUSION: We prepared the coating, which had both corrosion resistance and biological activity, on the surface of magnesium alloy by use of magnetron sputtering and alkali heat treatment technology. After soaking in the simulated body fluid for 24 hours and 168 hours, the deposition of the coating surface contained Ca, P products. Ca/P ratios were 1.54 and 2.11, respectively, closed to the bone-phosphate Ca/P ratio. The coating surface formed 5-10 μm pitting after 24 hours of immersion, and the pitting grew up with the immersion time. The pitting was enlarged to 100-800 μm after 168 hours.

Key words: biocompatible materials, corrosion, biodegradation, environmental, magnesium, fracture fixation

CLC Number:

R318

Zang Zhi-hai, Yin Dong-song, Xu Xiao-jing, Yin Qing-wei, Wang Li-gang, Liu Wen-jun . Corrosion behavior of Ti-Cu coating on the surface of bone magnesium alloy[J]. Chinese Journal of Tissue Engineering Research, 2013, 17(42): 7363-7368.

Figures/Tables 6

References

[1] 彭友霖,周丽丽,周艳红.镁合金作为生物医用植入材料的临床应用[J].中国组织工程研究与临床康复,2011,15(42):7923-7927.
[2] Witte F, Fischer J, Nellesen J, et al. In vitro and in vivo corrosion measurements of magnesium alloys. Biomaterials. 2006;27(7):1013-1018.
[3] Witte F, Kaese V, Haferkamp H, et al. In vivo corrosion of four magnesium alloys and the associated bone response. Biomaterials. 2005;26(17):3557-3563.
[4] 陈旭琼,尹庆水,张余,等.镁铝合金最大剂量的致敏试验[J].中国组织工程研究与临床康复,2010,14(16):2899-2900.
[5] Staiger MP, Pietak AM, Huadmai J, et al. Magnesium and its alloys as orthopedic biomaterials: a review. Biomaterials. 2006;27(9):1728-1734.
[6] 王飞,王钢,孟祥翔,等.新型镁合金皮内刺激与致敏实验研究[J].中国矫形外科杂志,2009,17(13):1013-1015.
[7] Zheng YF, Gu XN, Xi YL, et al. In vitro degradation and cytotoxicity of Mg/Ca composites produced by powder metallurgy. Acta Biomater. 2010;6(5):1783-1791.
[8] 葛淑萍,王贵学,沈阳,等.镁基合金应用于生物医用材料的研究进展[J].材料导报,2010,24(5):124-126.
[9] 李锴锴,王冰,严彪.镁合金作为生物医用材料的腐蚀与防护研究进展[J].腐蚀科学与防护技术,2012,24(3):181-184.
[10] 郑玉峰,顾雪楠,李楠,等.生物可降解镁合金的发展现状与展望[J].中国材料进展,2011,30(4):30-33.
[11] 陶冶,张永君.医用镁合金仿生钝化技术研究进展[J].电镀与涂饰,2012,31(3):39-42.
[12] 张广道. AZ31B生物可降解镁合金植入兔下颌骨生物学行为的实验研究[D].沈阳:中国医科大学,2009.
[13] 于国宁,张二林,徐丽萍.骨组织对镁合金植入材料的骨反应[C].北京:中国材料研究学会2006年会论文集,2006: 331-332.
[14] Witte F, Kaese V, Haferkamp H, et al. In vivo corrosion of four magnesium alloys and the associated bone response. Biomaterials. 2005;26(17):3557-3563.
[15] Peng Q, Huang Y, Zhou L, et al. Preparation and properties of high purity Mg-Y biomaterials. Biomaterials. 2010;31(3): 398-403.
[16] Gu X, Zheng Y, Cheng Y, et al. In vitro corrosion and biocompatibility of binary magnesium alloys. Biomaterials. 2009;30(4):484-498.
[17] Zhang EL, Yin DS, Xu LP, et al. Microstructure, mechanical and corrosion properties and biocompatibility of Mg–Zn–Mn alloys for biomedical application. Mater Sci Eng C. 2009;29(3): 987-993.
[18] Liu CL, Xin YC, TangGY．Influence of heat treatment on degradation behavior of bio-degradable die-cast AZ63 magnesium alloy in simulated body fluid．Mater Sci Eng A Struct Mater. 2006;456(1):350-357.
[19] Song Y, Zhang S, Li J, et al. Electrodeposition of Ca-P coatings on biodegradable Mg alloy: in vitro biomineralization behavior. Acta Biomater. 2010;6(5):1736-1742.
[20] Wang HX, Guan SK, Wang X, et al. In vitro degradation and mechanical integrity of Mg-Zn-Ca alloy coated with Ca-deficient hydroxyapatite by the pulse electrodeposition process. Acta Biomater. 2010;6(5):1743-1748.
[21] Song YW, Shan DY, Han EH. Electrodeposition of hydroxyapatite coating on AZ91D magnesium alloy for biomaterial application. Mater Lett. 2008;62(17-18): 3276-3279.
[22] Zhang EL , Xu LP, Yang K. Formation by ion plating of Ti-coating on pure Mg for biomedical applications. Scr Mater. 2005;53(5):523-527.
[23] 黄晶晶,任伊宾,张炳春,等.可降解镁植入材料表面涂层的制备及其性能[J].中国有色金属学报,2007,17(9):1466-1468.
[24] 徐丽萍,张二林,杨柯.医用镁合金表面磷化处理及生物腐蚀性能[J].电镀与精饰,2012,34(6):231-232.
[25] 高亚丽,熊党生.医用镁合金等离子喷涂羟基磷灰石涂层研究[J].材料热处理学报,2011,32(1):110-112.
[26] Wan YZ, Xiong GY, Luo HL, et al. Influence of zinc ion implantation on surface nanomechanical performance and corrosion resistance of biomedical magnesium–calcium alloys. Appl Surf Sci. 2008;254(17):5514-5516.
[27] Gu XN, Zheng W, Cheng Y, et al. A study on alkaline heat treated Mg-Ca alloy for the control of the biocorrosion rate. Acta Biomater. 2009;5(7):2790-2799.
[28] Tan LL, Wang Q, Geng F, et al. Preparation and characterization of Ca-P coating on AZ31 magnesium alloy. Trans Nonferrous Metals Society China. 2010;20(z2): 648-654.
[29] Yang JX, Cui FZ, Lee IS, et al. Plasma surface modification of magnesium alloy for biomedical application. Surf Coat Technol. 2010;205(S1):182-187.
[30] 王亚明,王福会,雷廷权,等.镁合金表面生物陶瓷涂层在模拟体液中的腐蚀性能[J].热处理技术与装备,2007,28(6):7-9.
[31] Shi P, Ng WF, Wong MH, et al. Improvement of corrosion resistance of pure magnesium in Hanks’ solution by microarc oxidation with sol–gel TiO2 sealing. J Alloys Compd. 2009; 469(1-2):286-292.
[32] Chen J, Zeng RC, Huang WJ, et al. Characterization and wear resistance of macro-arc oxidation coating on magnesium alloy AZ91 in simulated body fluids. Trans Nonferrous Metals Society China. 2008;18(S1):361-364.
[33] Lei T, Ouyang C, Tang W, et al. Enhanced corrosion protection of MgO coatings on magnesium alloy deposited by an anodic electrodeposition process. Corros Sci. 2010;52(10): 3504-3508.
[34] 李姝,董寅生,盛晓波,等.医用 AZ31 镁合金表面复合膜层的制备及其性能表征[J].表面技术,2010,39(1):41-44.
[35] Xu L, Pan F, Yu G, et al. In vitro and in vivo evaluation of the surface bioactivity of a calcium phosphate coated magnesium alloy. Biomaterials. 2009;30(8):1512-1523.
[36] 高亚丽,熊党生,王存山,等.医用镁合金激光熔覆羟基磷灰石涂层初探[J].特种铸造及有色合金,2009,29(4):304-306.
[37] 许鑫华,程静,张春怀,等.医用镁合金的生物腐蚀及高分子涂层处理[J].稀有金属材料与工程,2008,37(7):1225-1227.
[38] 颜廷亭,谭丽丽,熊党生,等.生物医用AZ31B 镁合金表面稀土转化膜的制备及其性能研究[J].稀有金属材料与工程,2009,38(5): 918-923.
[39] Witte F, Fischer J, Nellesen J, et al. In vivo corrosion and corrosion protection of magnesium alloy LAE442. Acta Biomater. 2010;6(5):1792-1799.
[40] Liu C L, Xin YC, Tian XB, et al. Corrosion resistance of titanium ion implanted AZ91 magnesium alloy. J Vac Sci Technol A. 2007;25(2):334-340.
[41] 国家质量监督检验检疫总局. GB/T 16886.15-2003/ISO 10993-15:2000 医疗器械生物学评价第15部分：金属与合金降解产物的定性与定量[S].北京:中国标准出版社.2003.
[42] 邹鹑鸣.钛丝烧结制备医用多孔钛及其表面Si-HA生物活化[D].哈尔滨:哈尔滨工业大学.2007.
[43] Kim HM, Takadama H, Kokubo T, et al. Formation of a bioactive graded surface structure on Ti-15Mo-5Zr-3Al alloy by chemical treatment. Biomaterials. 2000;21(4):353-358.