氧化时间对AZ31B镁合金微弧氧化涂层结构及性能的影响
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摘要
目的探索氧化时间对AZ31B镁合金表面微弧氧化(MAO)涂层结构及性能的影响规律。方法 通过恒压MAO的方法在硅酸盐电解液体系中制备涂层,采用扫描电子显微镜(SEM)、Image-J图像分析法、测厚仪、表面粗糙度仪、摩擦磨损试验机、盐雾试验箱来研究涂层表面微观形貌、表面孔隙率、厚度、粗糙度、摩擦性能以及耐蚀性能。结果涂层孔隙率随着氧化时间的延长而减小,氧化25 min所得涂层孔隙率最小,为5.404%。涂层厚度随时间的延长而增大,但是厚度增长速率减小,氧化5 min时涂层厚度为9μm,而25 min时涂层厚度为10.4μm。涂层粗糙度与摩擦系数随时间的增加而增大,磨损率随氧化时间的增加,呈现先增大后减小的趋势,氧化15 min所得样品磨损率最高,氧化5 min所得涂层耐蚀性最差,氧化25 min的涂层耐蚀性最好。结论恒压条件下,氧化时间的延长可以有效地减小涂层表面孔隙率,增加涂层厚度,显著改善涂层的耐磨、耐蚀性能。
The work aims to explore the effect of oxidation time on the structure and properties of micro-arc oxidation(MAO) coating on AZ31 B magnesium alloy. The coatings were prepared in the silicate electrolyte system by constant pressure MAO method. The micro-morphology, surface porosity, thickness, roughness, friction properties and corrosion resistance of the coatings were studied by scanning electron microscopy(SEM), Image-J analysis method, thickness gauge, surface roughness tester, material surface performance comprehensive tester and salt spray test. With the prolongation of oxidation time, the porosity of the coatings decreased and reached to the minimum value of 5.404% after 25 min of oxidation. The thickness of the coatings increased with the prolongation of oxidation time, but the growth rate of the thickness decreased. The thickness of the coatings was 9 μm after 5 min oxidation and 10.4 μm after 25 min oxidation. The roughness and friction coefficient of the coating increased as the time increased. With the increase of oxidation time, the wear rate firstly increased and then decreased. The wear rate of samples obtained after 15 minutes of oxidation was the highest; the corrosion resistance of coatings obtained after oxidation for 5 minutes was the worst, and that of coatings obtained after 25 minutes of oxidation was the best. Under constant pressure, the prolongation of oxidation time can effectively reduce the surface porosity of the coating, increase the thickness of the coating, and significantly improve the wear resistance and corrosion resistance of the coating.
The work aims to explore the effect of oxidation time on the structure and properties of micro-arc oxidation(MAO) coating on AZ31 B magnesium alloy. The coatings were prepared in the silicate electrolyte system by constant pressure MAO method. The micro-morphology, surface porosity, thickness, roughness, friction properties and corrosion resistance of the coatings were studied by scanning electron microscopy(SEM), Image-J analysis method, thickness gauge, surface roughness tester, material surface performance comprehensive tester and salt spray test. With the prolongation of oxidation time, the porosity of the coatings decreased and reached to the minimum value of 5.404% after 25 min of oxidation. The thickness of the coatings increased with the prolongation of oxidation time, but the growth rate of the thickness decreased. The thickness of the coatings was 9 μm after 5 min oxidation and 10.4 μm after 25 min oxidation. The roughness and friction coefficient of the coating increased as the time increased. With the increase of oxidation time, the wear rate firstly increased and then decreased. The wear rate of samples obtained after 15 minutes of oxidation was the highest; the corrosion resistance of coatings obtained after oxidation for 5 minutes was the worst, and that of coatings obtained after 25 minutes of oxidation was the best. Under constant pressure, the prolongation of oxidation time can effectively reduce the surface porosity of the coating, increase the thickness of the coating, and significantly improve the wear resistance and corrosion resistance of the coating.
引文
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[19]崔学军,王荣,魏劲松,等.电参数对AZ31B镁合金微弧氧化膜微观形貌及耐蚀性的影响[J].中国腐蚀与防护学报,2014,34(6):495-501.CUI Xue-jun,WANG Rong,WEI Jin-song,et al.Effect of electrical parameters on micromorphology and corrosion resistance of micro-arc oxidation coating on AZ31B mg alloy[J].Journal of Chinese society for corrosion&protection,2014,34(6):495-501.
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[21]崔学军,平静,窦宝捷,等.几种添加剂作用的微弧氧化膜表面结构及防腐性能[J].中国表面工程,2018,31(2):39-50.CUI Xue-jun,PING Jing,DOU Bao-jie,et al.Surface morphology and anti-corrosion of micro-arc oxidation coatings with different additives[J].China surface engineering,2018,31(2):39-50.
[22]崔学军,代鑫,郑冰玉,等.KH-550对AZ31B镁合金表面微弧氧化膜结构及性能的影响[J].中国腐蚀与防护学报,2017(3):35-40.CUI Xue-jun,DAI Xin,ZHENG Bing-yu,et al.Effect of KH-550 content on structure and properties of a micro-arc oxidation coating on mg-alloy AZ31B[J].Journal of Chinese society for corrosion&protection,2017(3):35-40.
[23]CURRAN J A,CLYNE T W.Porosity in plasma electrolytic oxide coatings[J].Acta materialia,2006,54(7):1985-1993.
[24]AGHION E,PEREZ Y.Effects of porosity on corrosion resistance of Mg alloy foam produced by powder metallurgy technology[J].Materials characterization,2014,96:78-83.
[25]NOTTER I M,GABE D R.Porosity of electrodeposited coatings:Its cause,nature,effect and management[J].Corrosion reviews,1992,10(3-4):217-280.
[26]DIETZEL W,KLAPKIV M,NYKYFORCHYN H,et al Porosity and corrosion properties of electrolyte plasma coatings on magnesium alloys[J].Materials science,2004,40(5):585-590.
[27]WALSH F C,LEóN C P D,KERR C,et al.Electrochemical characterisation of the porosity and corrosion resistance of electrochemically deposited metal coatings[J].Surface&coatings technology,2008,202(21):5092-5102.
[28]BLAWERT C,HEITMANN V,DIETZEL W,et al.Influence of electrolyte on corrosion properties of plasma electrolytic conversion coated magnesium alloys[J].Surface&coatings technology,2007,201(21):8709-8714.
[29]CUI L Y,ZENG R C,GUAN S K,et al.Degradation mechanism of micro-arc oxidation coatings on biodegradable Mg-Ca alloys:The influence of porosity[J].Journal of alloys&compounds,2017,695:2464-2476.
[30]LU X P,BLAWERT C,TOLNAI D,et al.3D reconstruction of plasma electrolytic oxidation coatings on mg alloy via synchrotron radiation tomography[J].Corrosion science,2018,139:395-402.
[31]吕维玲.AZ91D镁合金微弧氧化膜制备的调控及膜层表征方法的研究[D].兰州:兰州理工大学,2010.LYU Wei-ling.Control principle of fabrication and characterization for micro-structure and properties of microarc oxidation coating on AZ91D magnesium alloys[D].Lanzhou:Lanzhou University of Technology,2010.
[32]CURRAN J A,CLYNE T W.Porosity in plasma electrolytic oxide coatings[J].Acta materialia,2006,54(7):1985-1993.
[33]ONO S,MORONUKI S,MORI Y,et al.Effect of electrolyte concentration on the structure and corrosion resistance of anodic films formed on magnesium through plasma electrolytic oxidation[J].Electrochimica acta,2017,240:415-423.
[34]ZHANG D Y,GE Y F,LIU G L,et al.Investigation of tribological properties of micro-arc oxidation ceramic coating on Mg alloy under dry sliding condition[J].Ceramic international,2018,44(14):16164-16172.
[35]GUO H X,YING M A,WANG J S,et al.Corrosion behavior of micro-arc oxidation coating on AZ91D magnesium alloy in NaCl solutions with different concentrations[J].Transactions of nonferrous metals society of China,2012,22(7):1786-1793.
[36]DONG K,SONG Y,SHAN D,et al.Formation mechanism of a self-sealing pore micro-arc oxidation film on AM60 magnesium alloy[J].Corrosion science,2015,100:275-283.
[2]YANG W,WANG J L,XU D P,et al.Characterization and formation mechanism of grey micro-arc oxidation coatings on magnesium alloy[J].Surface and coatings technology,2015,283:281-285.
[3]CUI X J,YANG R S,LIU C H,et al.Structure and corrosion resistance of modified micro-arc oxidation coating on AZ31B magnesium alloy[J].Transactions of nonferrous metals society of China,2016(26):814-821.
[4]GUO H F,AN M Z.Growth of ceramic coatings on AZ91Dmagnesium alloys by micro-arc oxidation in aluminatefluoride solutions and evaluation of corrosion resistance[J].Applied surface science,2005,246(1-3):229-238.
[5]MUHAFFEL F,CIMENOGLU H.Development of corrosion and wear resistant micro-arc oxidation coating on a magnesium alloy[J].Surface&coatings technology,2019,357:822-832.
[6]WALTER R,KANNAN M B.Influence of surface roughness on the corrosion behaviour of magnesium alloy[J].Materials and design,2011,32(4):2350-2354.
[7]WANG J H,DU M H,HAN F Z,et al.Effects of the ratio of anodic and cathodic currents on the characteristics of micro-arc oxidation ceramic coatings on Al alloys[J].Applied surface science,2014,292:658-664.
[8]DA F A,BESTETTI M.Effect of the electrolytic solution composition on the performance of micro-arc anodic oxidation films formed on AM60B magnesium alloy[J].Surface&coatings technology,2010,205(6):1783-1788.
[9]WANG X,ZHU Z,LI Y,et al.Characterization of micro-arc oxidation coatings on 6N01 aluminum alloy under different electrolyte temperature control modes[J].Journal of materials engineering&performance,2018,27(4):1-8.
[10]WANG J L,YANG W,XU D P,et al.Effect of K2TiO(C2O4)2 addition in electrolyte on the microstructure and tribological behavior of micro-arc oxidation coatings on aluminum alloy[J].Acta metallurgica sinica(english letters),2017,30(11):79-88.
[11]XU L,WU C,LEI X,et al.Effect of oxidation time on cytocompatibility of ultrafine-grained pure Ti in micro-arc oxidation treatment[J].Surface&coatings technology,2018,342:12-22.
[12]ZHANG J,FAN Y,ZHAO X,et al.Influence of duty cycle on the growth behavior and wear resistance of micro-arc oxidation coatings on hot dip aluminized cast iron[J].Surface and coatings technology,2017,337:141-149.
[13]吴振东,姜兆华,姚忠平,等.反应时间对LY12铝合金微弧氧化膜层组织及性能的影响[J].无机材料学报,2007,22(3):555-559.WU Zhen-dong,JIANG Zhao-hua,YAO Zhong-ping,et al.Influence of treatment time on structure and property of ceramic coatings formed on LY12 aluminum alloy by micro-arc oxidation[J].Journal of inorganic materials,2007,22(3):555-559.
[14]闫凤英,石玉龙,莫伟言.氧化时间对钛表面微弧氧化膜层的影响[J].表面技术,2010,39(4):42-44.YAN Feng-ying,SHI Yu-long,MO Wei-yan,Influence of oxidation time on micro-arc oxidation coating on Ti tanium substrate[J].Surface technology,2010,39(4):42-44.
[15]吕维玲,马颖,陈体军,等.氧化时间对AZ91D镁合金微弧氧化膜微观组织和性能的影响[J].中国有色金属学报,2009,19(8):1385-1391.LV Wei-ling,MA Ying,CHEN Ti-jun,et al.Effects of oxidation time on microstructures and properties of micro-arc oxidation coatings of AZ91D magnesium alloy[J].Transactions of nonferrous metals society of China,2009,19(8):1385-1391.
[16]董凯辉,宋影伟,单大勇,等.镁合金微弧氧化技术的研究进展[J].表面技术,2015,44(3):74-80.DONG Kai-hui,SONG Ying-wei,SHAN Da-yong,et al.Research progress of micro-arc oxidation technology on magnesium alloys[J].Surface technology,2015,44(3):74-80.
[17]QIAN B Y,MIAO W,QIU M,et al.Influence of voltage on the corrosion and wear resistance of micro-arc oxidation coating on Mg-8Li-2Ca alloy[J].Acta metallurgica sinica(english letters),2019,32(2):194-204.
[18]杨瑞嵩,魏劲松,崔学军.AZ91D镁合金恒功率微弧氧化膜的结构及耐蚀性能[J].材料保护,2015,48(12):8-11.YANG Rui-song,WEI Jin-song,CUI Xue-jun.Structure and corrosion resistance of constant power micro-arc oxidation film on AZ91D magnesium Alloy[J].Materials protection,2015,48(12):8-11.
[19]崔学军,王荣,魏劲松,等.电参数对AZ31B镁合金微弧氧化膜微观形貌及耐蚀性的影响[J].中国腐蚀与防护学报,2014,34(6):495-501.CUI Xue-jun,WANG Rong,WEI Jin-song,et al.Effect of electrical parameters on micromorphology and corrosion resistance of micro-arc oxidation coating on AZ31B mg alloy[J].Journal of Chinese society for corrosion&protection,2014,34(6):495-501.
[20]崔学军,平静.微弧氧化及其在镁合金腐蚀防护领域的研究进展[J].中国腐蚀与防护学报,2018,38(2):3-20.CUI Xue-jun,PING Jing.Research progress of micro-arc oxidation for corrosion prevention of Mg-alloys[J].Journal of Chinese society for corrosion&protection,2018,38(2):3-20.
[21]崔学军,平静,窦宝捷,等.几种添加剂作用的微弧氧化膜表面结构及防腐性能[J].中国表面工程,2018,31(2):39-50.CUI Xue-jun,PING Jing,DOU Bao-jie,et al.Surface morphology and anti-corrosion of micro-arc oxidation coatings with different additives[J].China surface engineering,2018,31(2):39-50.
[22]崔学军,代鑫,郑冰玉,等.KH-550对AZ31B镁合金表面微弧氧化膜结构及性能的影响[J].中国腐蚀与防护学报,2017(3):35-40.CUI Xue-jun,DAI Xin,ZHENG Bing-yu,et al.Effect of KH-550 content on structure and properties of a micro-arc oxidation coating on mg-alloy AZ31B[J].Journal of Chinese society for corrosion&protection,2017(3):35-40.
[23]CURRAN J A,CLYNE T W.Porosity in plasma electrolytic oxide coatings[J].Acta materialia,2006,54(7):1985-1993.
[24]AGHION E,PEREZ Y.Effects of porosity on corrosion resistance of Mg alloy foam produced by powder metallurgy technology[J].Materials characterization,2014,96:78-83.
[25]NOTTER I M,GABE D R.Porosity of electrodeposited coatings:Its cause,nature,effect and management[J].Corrosion reviews,1992,10(3-4):217-280.
[26]DIETZEL W,KLAPKIV M,NYKYFORCHYN H,et al Porosity and corrosion properties of electrolyte plasma coatings on magnesium alloys[J].Materials science,2004,40(5):585-590.
[27]WALSH F C,LEóN C P D,KERR C,et al.Electrochemical characterisation of the porosity and corrosion resistance of electrochemically deposited metal coatings[J].Surface&coatings technology,2008,202(21):5092-5102.
[28]BLAWERT C,HEITMANN V,DIETZEL W,et al.Influence of electrolyte on corrosion properties of plasma electrolytic conversion coated magnesium alloys[J].Surface&coatings technology,2007,201(21):8709-8714.
[29]CUI L Y,ZENG R C,GUAN S K,et al.Degradation mechanism of micro-arc oxidation coatings on biodegradable Mg-Ca alloys:The influence of porosity[J].Journal of alloys&compounds,2017,695:2464-2476.
[30]LU X P,BLAWERT C,TOLNAI D,et al.3D reconstruction of plasma electrolytic oxidation coatings on mg alloy via synchrotron radiation tomography[J].Corrosion science,2018,139:395-402.
[31]吕维玲.AZ91D镁合金微弧氧化膜制备的调控及膜层表征方法的研究[D].兰州:兰州理工大学,2010.LYU Wei-ling.Control principle of fabrication and characterization for micro-structure and properties of microarc oxidation coating on AZ91D magnesium alloys[D].Lanzhou:Lanzhou University of Technology,2010.
[32]CURRAN J A,CLYNE T W.Porosity in plasma electrolytic oxide coatings[J].Acta materialia,2006,54(7):1985-1993.
[33]ONO S,MORONUKI S,MORI Y,et al.Effect of electrolyte concentration on the structure and corrosion resistance of anodic films formed on magnesium through plasma electrolytic oxidation[J].Electrochimica acta,2017,240:415-423.
[34]ZHANG D Y,GE Y F,LIU G L,et al.Investigation of tribological properties of micro-arc oxidation ceramic coating on Mg alloy under dry sliding condition[J].Ceramic international,2018,44(14):16164-16172.
[35]GUO H X,YING M A,WANG J S,et al.Corrosion behavior of micro-arc oxidation coating on AZ91D magnesium alloy in NaCl solutions with different concentrations[J].Transactions of nonferrous metals society of China,2012,22(7):1786-1793.
[36]DONG K,SONG Y,SHAN D,et al.Formation mechanism of a self-sealing pore micro-arc oxidation film on AM60 magnesium alloy[J].Corrosion science,2015,100:275-283.