TA15合金微弧氧化陶瓷涂层制备与电偶腐蚀性能
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摘要
目的改善TA15合金(Ti6Al2Zr1Mo1V)与异种金属间接触时产生的电偶腐蚀性能。方法 采用微弧氧化(Microarc oxidation,MAO)方法在硅酸盐电解液中,于钛合金表面制备Ti O_2基陶瓷涂层。采用XRD、SEM和EDS等方法 ,表征涂层的物相成分、组织结构及元素分布,用极化曲线、电化学阻抗谱和电偶腐蚀等测试涂层的耐腐蚀性能。结果微弧氧化涂层由内外两层组成,内层致密,外层疏松多微孔,且内层与基体的结合呈现凹凸界面,出现"局部过生长"现象。涂层以金红石和锐钛矿Ti O_2相为主。与基体合金相比,陶瓷涂层的自腐蚀电位提高了0.672 V;随氧化时间的延长,涂层厚度增加,内层变得更加致密,涂层的自腐蚀电位提高。涂层内层的阻抗模值,随氧化时间的增加而增大,分别为1.16×10~6Ω·cm~2(10 min)、1.2×10~6Ω·cm~2(30 min)和3.8×10~6Ω·cm~2(50 min)。在3.5%NaCl溶液中进行电偶腐蚀试验15天后,30CrMnSiA钢/TA15合金微弧氧化涂层对偶件的平均电偶腐蚀速度,明显低于30CrMnSiA钢与TA15合金、巴氏合金、铝青铜偶接时的腐蚀速度。结论微弧氧化致密阻挡层具有良好的阻隔特性,降低了电偶腐蚀敏感度,有效缓解了电偶腐蚀的发生。
The work aims to alleviate the galvanic corrosion between TA15 alloy(Ti6Al2Zr1Mo1V) and dissimilar metals caused by contact. TiO_2 ceramic coating was fabricated on the surface of titanium alloy by microarc oxidation(MAO) method in silicate based electrolyte. The phase composition, microstructure and distribution of element of the coatings were characterized by characterization methods such as XRD, SEM and EDS, and the corrosion resistance was investigated by polarization curves,electrochemical impedance spectrum(EIS) and galvanic corrosion. The MAO coating was composed of inner layer and outer layer. The inner layer was dense, while the outer layer was loose and microporous. The bonding of the inner layer and matrix showed a concave and convex interface, and the phenomenon of ‘local over-growth' appeared in some local regions. The coating mainly consisted of rutile and anatase TiO_2. Compared with matrix alloy, the self-corrosion potential of the coating was increased by 0.672 V. Meanwhile, with the oxidation time increasing, the coating thickness increased and the inner layer became denser, which improved the self-corrosion potential of the coating. As the increase of oxidation time, the impedance of the inner layer increased, which was 1.16×10~6 Ω·cm~2(10 min), 1.2×10~6 Ω·cm~2(30 min), and 3.8×10~6 Ω·cm~2(50 min), respectively. After galvanic corrosion testing for 15 days in 3.5 wt.% NaCl solution, the average galvanic corrosion rate of steel/MAO coating on TA15 alloy was significantly lower than the corrosion rate of 30 CrMnSiA steel coupled with TA15 alloy, babbitt and albronze.The excellent dense barrier inner layer of the MAO coatings has good blocking features and reduces the galvanic corrosion sensitivity, thus effectively alleviating the occurrence of galvanic corrosion.
The work aims to alleviate the galvanic corrosion between TA15 alloy(Ti6Al2Zr1Mo1V) and dissimilar metals caused by contact. TiO_2 ceramic coating was fabricated on the surface of titanium alloy by microarc oxidation(MAO) method in silicate based electrolyte. The phase composition, microstructure and distribution of element of the coatings were characterized by characterization methods such as XRD, SEM and EDS, and the corrosion resistance was investigated by polarization curves,electrochemical impedance spectrum(EIS) and galvanic corrosion. The MAO coating was composed of inner layer and outer layer. The inner layer was dense, while the outer layer was loose and microporous. The bonding of the inner layer and matrix showed a concave and convex interface, and the phenomenon of ‘local over-growth' appeared in some local regions. The coating mainly consisted of rutile and anatase TiO_2. Compared with matrix alloy, the self-corrosion potential of the coating was increased by 0.672 V. Meanwhile, with the oxidation time increasing, the coating thickness increased and the inner layer became denser, which improved the self-corrosion potential of the coating. As the increase of oxidation time, the impedance of the inner layer increased, which was 1.16×10~6 Ω·cm~2(10 min), 1.2×10~6 Ω·cm~2(30 min), and 3.8×10~6 Ω·cm~2(50 min), respectively. After galvanic corrosion testing for 15 days in 3.5 wt.% NaCl solution, the average galvanic corrosion rate of steel/MAO coating on TA15 alloy was significantly lower than the corrosion rate of 30 CrMnSiA steel coupled with TA15 alloy, babbitt and albronze.The excellent dense barrier inner layer of the MAO coatings has good blocking features and reduces the galvanic corrosion sensitivity, thus effectively alleviating the occurrence of galvanic corrosion.
引文
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[2]BOYER R R.An overview on the use of titanium in the aerospace industry[J].Materials science and engineering:A,1996,213(1-2):103-114.
[3]李兴元,沙爱学,张旺峰,等.TA15合金及其在飞机结构中的应用前景[J].钛工业进展,2003(Z1):90-94.LI Xing-yuan,SHA Ai-xue,ZHANG Wang-feng,et al.TA15 titanium alloy and its applying prospects on airframe[J].Titanium industry progress,2003(Z1):90-94.
[4]王桂生.Ti-6Al-2Zr-1Mo-1V合金组织与性能的研究[J].稀有金属,1995(5):352-356.WANG Gui-sheng.Study on microstructure and properties of Ti-6Al-2Zr-1Mo-1V alloy[J].Rare metal,1995(5):352-356.
[5]赵晴,朱文辉,王帅星.微弧氧化TC4钛合金与金属电偶的腐蚀行为[J].材料保护,2011,44(4):7-10.ZHAO Qing,ZHU Wen-hui,WANG Shuai-xing.Galvanic corrosion behavior of micro-arc oxidation coating on TC4 titanium alloy coupled with metals[J].Materials protection,2011,44(4):7-10.
[6]张鹏飞.TA15合金经微弧氧化后的腐蚀与疲劳性能[D].哈尔滨:哈尔滨工业大学,2008.ZHANG Peng-fei.Corrosion and fatigue properties of TA15 alloy coated by microarc oxidation[D].Harbin:Harbin Institute of Technology,2008.
[7]WANG S,WANG Y,CUI Y,et al.High voltage resistance ceramic coating fabricated on titanium alloy for insulation shielding application[J].Ceramics international,2019,45(2):1909-1917.
[8]SOMSANITH N,NARAYANANT S N S,KIM Y K,et al.Surface medication of Ti-15Mo alloy by thermal oxidation:Evaluation of surface characteristics and corrosion resistance in Ringer's solution[J].Applied surface science,2015,356:1117-1126.
[9]UNAL O,MALEKI E,VAROL R.Effect of severe shot peening and ultra-low temperature plasma nitriding on Ti-6Al-4V alloy[J].Vacuum,2018,150:69-78.
[10]YAO Q,SUN J,ZHANG G,et al.Enhanced toughness of nitrided layers formed on Ti-6Al-4V alloy via surface mechanical attrition pre-treatment[J].Vacuum,2017,142:45-51.
[11]JU R,YUAN W,RUYAN L,et al.Interface structure between titanium substrate and high temperature oxidation resistant aluminum-base coatings[J].Rare metal materials and engineering,2018,47(2):682-686.
[12]FAZEL M,SALIMIJAZI H R,SHAMANIAN M.Improvement of corrosion and tribocorrosion behavior of pure titanium by subzero anodic spark oxidation[J].ACSapplied materials&interfaces,2018,10(17):15281-15287.
[13]JEONG C,LEE J,SHEPPARD K,et al.Air-impregnated nanoporous anodic aluminum oxide layers for enhancing the corrosion resistance of aluminum[J].Langmuir,201531(40):11040-11050.
[14]YEROKHIN A L,NIE X,LEYLAND A,et al.Plasma electrolysis for surface engineering[J].Surface and coatings technology,1999,122(2-3):73-93.
[15]王亚明,邹永纯,王树棋,等.金属微弧氧化功能陶瓷涂层设计制备与使役性能研究进展[J].中国表面工程,2018,31(4):20-45.WANG Ya-ming,ZOU Yong-chun,WANG Shu-qi,et al.Design,fabrication and performance of multifuctional ceramic coatings formed by microarc oxidation on metals:A critial review[J].China surface engineering,2018,31(4):20-45.
[16]房爱存,解光胜.微弧氧化技术在铝、镁及其合金海洋环境防腐蚀中的应用[J].表面技术,2012,41(1):54-57.FANG Ai-cun,XIE Guang-sheng.Application of micro-arc oxidation technology in aluminum,magnesium and its alloys against corrosion in the marine environment[J].Surface technology,2012,41(1):54-57.
[17]QIN D,XU G,YANG Y,et al.Multiphase ceramic coatings with high hardness and wear resistance on 5052 aluminum alloy by a microarc oxidation method[J].ACSsustainable chemistry&engineering,2018,6(2):2431-2437.
[18]FAZEL M,SALIMIJAZI H R,GOLOZAR M A.Acomparison of corrosion,tribocorrosion and electrochemical impedance properties of pure Ti and Ti6Al4Valloy treated by micro-arc oxidation process[J].Applied surface science,2015,324:751-756.
[19]ZENG R C,CUI L,JIANG K,et al.In vitro corrosion and cytocompatibility of a microarc oxidation coating and poly(l-lactic acid)composite coating on Mg-1Li-1Ca alloy for orthopedic implants[J].ACS Applied materials&interfaces,2016,8(15):10014-10028.
[20]HE S,MA Y,YE H,et al.Ceramic oxide coating formed on beryllium by micro-arc oxidation[J].Corrosion science,2017,122:108-117.
[21]周鹏,林乃明,田伟,等.TC4合金微弧氧化层的耐磨性和耐蚀性[J].表面技术,2015,44(11):14-20.ZHOU Peng,LIN Nai-ming,TIAN Wei,et al.Wear and corrosion resistance of microarc oxidation coatings on TC4 alloy[J].Surface technology,2015,44(11):14-20.
[22]王琪超,杜楠,王帅星,等.Ti6Al4V微弧氧化TiO2/W复合膜的制备及摩擦学性能[J].表面技术,2019(1):191-199.WANG Qi-chao,DU Nan,WANG Shuai-xing,et al.Preparation and tribological property of TiO2/W composite coating on Ti6Al4V by micro-arc oxidation[J].Surface technology,2019(1):191-199.
[23]崔叶,蔡振兵,刘新龙,等.氧化时间对微弧氧化膜电接触微动磨损行为的影响[J].表面技术,2018,47(6):188-194.CUI Ye,CAI Zhen-bing,LIU Xin-long,et al.Effects of oxidation time on electrical contact fretting wear behavior of MAO(micro-arc oxidation)coating[J].Surface technology,2018,47(6):188-194.
[24]刘国宇,鲍崇高,张安峰.不锈钢与碳钢的液固两相流冲刷腐蚀磨损研究[J].材料工程,2004(11):37-40.LIU Guo-yu,BAO Cong-gao,ZHANG An-feng.Study on erosion-corrosion property of metal material[J].Materials engineering,2004(11):37-40.
[25]田永芹,常炜,胡丽华,等.APIX65、316L不锈钢及Inconel 625间电偶腐蚀风险研究[J].表面技术,2016,45(5):128-134.TIAN Yong-qin,CHANG Wei,HU Li-hua,et al.Risk of galvanic corrosion among API X65,316L and Inconel625[J].Surface technology,2016,45(5):128-134.
[26]杜敏,郭庆锟,周传静.碳钢/Ti和碳钢/Ti/海军黄铜在海水中电偶腐蚀的研究[J].中国腐蚀与防护学报,2006(5):263-266.DU Min,GUO Qing-kun,ZHOU Chuan-jing.Galvanic corrosion of carbon steel/titanium and carbon steel/titanium/navel brass in seawater[J].Journal of Chinese society for corrosion and protection,2006(5):263-266.
[27]梁健,顾艳红,杨远航,等.微弧氧化处理对铝合金钻杆与钢接头电偶腐蚀行为的影响[J].材料保护,2018,51(6):110-114.LIAN Jian,GUO Yan-hong,YANG Yuan-hang,et al.Effects of micro-arc oxidation treatment on galvanic corrosion behavior between aluminum alloy drill pipe and steel joints[J].Materials protection,2018,51(6):110-114.
[28]王玲,张巍,李久青,等.镁合金微弧氧化及涂装耐电偶腐蚀的研究[J].材料保护,2005(4):12-14.WANG Ling,ZHANG Wei,LI Jiu-qing,et al.Galvanic corrosion resistance of magnesium alloy with microarc oxidation film and coating[J].Materials protection2005(4):12-14.
[29]周吉学,陈燕飞,宋晓村,等.AZ31B镁合金/6061铝合金异质金属连接件整体微弧氧化膜的制备及其结构[J].机械工程材料,2018,42(5):20-26.ZHOU Ji-xue,CHEN Yan-fei,SONG Xiao-cun,et al.Preparation and structure of overall micro-arc oxidation film on AZ31B magnesium alloy/6061 aluminum alloy dissimilar metal connected part[J].Materials for mechanical engineering,2018,42(5):20-26.
[30]刘建华,吴昊,李松梅,等.表面处理对TC2钛合金电偶腐蚀的影响[J].腐蚀科学与防护技术,2003(1):13-17.LIU Jian-hua,WU Hao,LI Song-mei,et al.Effect of surface treatment on galvanic corrosion behavior of titanium alloy TC2 coupled with aluminum alloy and steels[J].Corrosion science and protection technology,2003(1):13-17.
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