镧铈混合稀土对AM60B镁合金电化学行为的影响
Effect of Lanthanum-Cerium Mixed Rare Earth on Electrochemical Behavior of AM60B Magnesium Alloy
摘要: 本文采用析氢实验、Mott-Schottky分析和电化学测试技术研究了3.5% NaCl溶液中La、Ce混合稀土对AM60B镁合金电化学性能的影响,并探讨其作用机理。结果表明,AM60B镁合金的析氢腐蚀电流密度降低、腐蚀电位升高、腐蚀电流密度降低、容抗弧值增大、电荷反应电阻Rct增大、双电层电容Cdl降低,镁合金的电化学性能提高,其原因归结于添加的La、Ce混合稀土元素细化了α-Mg晶粒、减弱了β相的电偶腐蚀作用,加之镁合金表面形成致密的La2O3和CeO2复合氧化膜,有效地阻隔Cl−向镁合金表面渗入,抑制了镁合金的溶解。Mott-Schottky曲线测试结果表明,少量添加La、Ce混合稀土AM60B镁合金在−1.9 V~−1.0 V的电位区间曲线呈线性,呈n-型半导体特征,供体密度ND减小,平带电位EFB负向移动,添加稀土La、Ce的镁合金耐蚀性得到提高。
Abstract: The effect of La, Ce mixed rare earth in 3.5% NaCl solution on the electrochemical properties of AM60B magnesium alloy was studied by hydrogen evolution experiment, Mott-Schottky analysis and electrochemical test, and its mechanism was discussed. The results show that the hydrogen evolution corrosion current density of AM60B magnesium alloy decreases; the corrosion potential increases; the corrosion current density decreases; the capacitance arc value increases; the charge reaction resistance Rct increases; and the double layer capacitance Cdl decreases, which improves the electrochemical properties of magnesium alloy, which is due to the addition of La, Ce mixed rare earth elements to refine α-Mg grain and weaken the galvanic corrosion of β phase. The occasional corrosion, coupled with the formation of dense La2O3 and CeO2 composite oxide films on the surface of magnesium alloy, effectively blocks the infiltration of Cl− into the surface of magnesium alloy and suppresses the dissolution of magnesium alloy. The results of Mott-Schottky curve show that the potential range curve of a small amount of La, Ce mixed rare earth AM60B magnesium alloy is linear in the range of −1.9V - −1.0V, showing n-type semiconductor characteristics; the donor density ND decreases and the flat band potential EFB moves negatively. The corrosion resistance of magnesium alloy with rare earth La, Ce was improved.
文章引用:黄乃宝, 邱忠瑜, 任婧, 梁成浩. 镧铈混合稀土对AM60B镁合金电化学行为的影响[J]. 材料科学, 2019, 9(10): 923-933. https://doi.org/10.12677/MS.2019.910114

参考文献

[1] Henderson, S.E., Verdelis, K., Maiti, S., et al. (2014) Magnesium Alloys as Abiomaterial for Degradable Craniofacial Screws. Acta Biomaterialia, 10, 2323-2332. [Google Scholar] [CrossRef] [PubMed]
[2] Dinodi, N. and Shett, A.N. (2014) Investigation of Influence of Medium pH and Sulfate Ion Concentrations on Corrosion Behavior of Magnesium Alloy ZE41. Surface Engineering and Applied Electrochemistry, 50, 149-156. [Google Scholar] [CrossRef] 
[3] Xie, S.Y., Peng, X.D., Li, J.C., et al. (2014) Microstructure and Corrosion Resistance of Mg-5Al-1Sr-2Ca-xY Alloy. Rare Metal Materials and Engineering, 43, 52-56. [Google Scholar] [CrossRef] 
[4] 王武孝, 刘雪雍, 王娜, 等. 超声处理对Mg-9Al-Zn-0.6Ce-1.2Ca镁合金组织及耐蚀性的影响[J]. 材料热处理学报, 2019, 40(1): 44-49.
[5] Holly, J., Hor-stemeyera, M. and Wang, P. (2010) Comparison of Corrosion Pitting under Immersion and Salt-Spray Environment an ASCAST AE44 Magnesium Alloy. Corrosion Science, 52, 3624-3627. [Google Scholar] [CrossRef] 
[6] 周京, 冯芝勇, 张金玲, 等. La含量对AZ91镁合金耐蚀性能的影响[J]. 太原理工大学学报, 2013, 44(5): 573-578.
[7] 王文礼, 雷宁宁, 邱玉龙, 等. 合金元素Ce对Mg-Y-Zr稀土镁合金显微组织和力学性能的影响[J]. 稀有金属, 2018, 42(4): 438-442.
[8] 李慧明, 谢刚, 李荣兴, 等. 稀土镁合金、AZ31及AZ91负极材料耐腐蚀性能及放电行为的比较[J]. 热加工工艺, 2018, 47(10): 57-60.
[9] Wang, J., Li, Y., Huang, S., et al. (2014) Effects of Y on the Microstructure, Mechanical and Bio-Corrosion Properties of Mg-Zn-Ca Bulk Metallic Glass. Journal of Materials Science and Technology, 30, 1255-1261. [Google Scholar] [CrossRef] 
[10] Zhang, J., Xu, M., Teng, X., et al. (2016) Effect of Gd Addition on Microstructure and Corrosion Behaviors of Mg-Zn-Y Alloy. Journal of Magnesium and Alloys, 4, 319-325. [Google Scholar] [CrossRef] 
[11] 张东阳, 王林生, 郭斗斗. 稀土镁合金性能研究及应用[J]. 材料导报, 2015, 29(12): 514-516.
[12] 余琨, 黎文献, 王日初, 等. 稀土Ce和Nd对AZ31镁合金耐蚀性能的影响[J]. 材料保护, 2007, 40(11): 6-9.
[13] 刘文娟, 曹发和, 张昭, 等. 稀土元素Ce和La合金化对AM 60镁合金腐蚀行为的影响[J]. 腐蚀科学与防护技术, 2009, 21(2): 82-84.
[14] 李瑛, 张涛, 王福会. AZ91D镁合金手汗腐蚀机理研究I.手汗模拟液中AZ91D镁合金腐蚀的动力学规律[J]. 中国腐蚀与防护学报, 2004, 24(5): 276-279.
[15] 李建兴, 张源, 李静媛. 微量CaO对Mg-2Zn-0.5Sr医用镁合金显微组织、力学性能及康腐蚀性能的影响[J]. 稀有金属材料与工程, 2019, 48(2): 463-471.
[16] 周苗, 刘楚明, 高永浩, 等. 含铜AZ31镁合金的腐蚀行为[J]. 中国有色金属学报, 2019, 29(1): 18-25.
[17] Liang, C.H., Wang, S.S., Huang, N.B., et al. (2015) Effects of Lanthanum and Cerium Mixed Rare Earth Metal on Abrasion and Corrosion Resistance of AM60 Magnesium Alloy. Rare Metal Materials and Engineering, 44, 521-526. [Google Scholar] [CrossRef] 
[18] 苏娟, 郭锋, 蔡会生, 等. 含铈AZ91镁合金的元素分布和组织结构研究[J]. 稀有金属材料与工程, 2018, 47(11): 3409-3413.
[19] Liu, S.F., Li, B., Wang, X.H., et al. (2009) Refinement Effect of Cerium, Calcium and Strontium in AZ91 Magenesium Alloy. Journal of Materials Processing Technology, 209, 3999-4004. [Google Scholar] [CrossRef] 
[20] 武枭伟, 周洋, 陈峰, 等. Nb添加对Ti基非晶合金腐蚀及力学性能的影响[J]. 材料科学与工艺, 2019, 27(2): 73-80.
[21] Li, Y., Zhang, T. and Wang, F.H. (2004) Corro-sion Behavior of AZ91D Magnesium Alloy in Hand Sweat. Corrosion and Protection, 24, 339-344.
[22] Liang, C.H., Zheng, R.F. and Huang, N.B. (2009) Conversion Coating Treatment for AZ31 Magnesium Alloys by a Phytic Acid Bath. Journal of Applied Electrochemistry, 39, 1857-1862. [Google Scholar] [CrossRef] 
[23] 冯艳, 刘莉, 殷立勇, 等. 稀土元素La对Mg-6Al-5Pb镁合金组织和腐蚀电化学行为的影响[J]. 中国有色金属学报, 2015, 25(10): 2623-2331.
[24] 雷黎, 王昕, 徐海港. 镁合金铈转化膜在NaCl溶液中的腐蚀行为及腐蚀机理[J]. 中国有色金属学报, 2015, 25(1): 125-132.
[25] 周琼宇, 盛敏奇, 钟庆东, 等. 镁合金在含F−的NaOH溶液中钝化行为的电化学研究[J]. 化学学报, 2010, 68(15): 1487-1493.
[26] Ningshen, S., Kamachi Mudali, U., Mittal, V.K., et al. (2007) Semiconducting and Passive Film Properties of Nitrogen-Containing Type 316LN Stainless Steel. Corrosion Science, 49, 481-496. [Google Scholar] [CrossRef] 
[27] 刘渝萍, 宋卫华, 陈昌国, 等. AZ31镁合金阳极氧化膜在3.5% NaCl溶液中不同浸泡时间的腐蚀机制[J]. 材料保护, 2013, 46(1): 8-12.