挤压对Mg-10Li-5Al-0.02Zr合金腐蚀行为的影响
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摘要
采用X射线衍射(XRD)、电子探针(EPMA)、扫描电子显微镜(SEM)和X射线光电子能谱(XPS)研究挤压前后Mg-10Li-5Al-0.02Zr合金的微观组织及合金在3.5%NaCl(质量分数)溶液中的析氢和电化学腐蚀行为,并分析腐蚀膜结构。结果表明:Mg-Li-Al-Zr合金热挤压后物相由α-Mg相、不规则的AlLi相、弥散的MgLi_2Al和β-Li基体组成。热挤压后,合金组织均匀,晶粒细化,第二相数量减少。铸态和挤压态样品的腐蚀速率(PH)分别为(2.74±0.2) mm/a和(1.47±0.2) mm/a,沿挤压方向形成的不连续带状组织和均匀组织减弱微电偶腐蚀,提高合金的耐蚀性。挤压态Mg-Li-Al-Zr合金在NaCl溶液中浸泡时,表面形成一层较致密的腐蚀表面膜,其由Mg(OH)_2、LiOH、Li_2CO_3和MgO构成。
Microstructure of Mg-10Li-5Al-0.02Zr alloy and the effects of extrusion on hydrogen and electrochemical corrosion behavior of Mg-Li-Al-Zr alloy in 3.5% NaCl(mass fraction) solution and the corrosion film structure were studied by X-ray diffractometry(XRD), electron probe micro-analyze(EPMA), scanning electron microscopy(SEM) and X-ray photoelectron spectroscopy(XPS). The results indicate that the Mg-Li-Al-Zr alloy after extrusion consists mainly of α-Mg, irregular AlLi, dispersed MgLi_2Al and β-Li phases. After extrusion, the structure of Mg-Li-Al-Zr alloy becomes more evenly, the grain size of Mg-Li-Al-Zr alloy refines, the number of second phases decreases. The average corrosion rates(PH) of Mg-Li-Al-Zr alloys before and after extrusion are(2.74±0.2) mm/a and(1.47±0.2) mm/a, respectively. A discontinuous banded structure forming along the extrusion direction and the uniform microstructure can weaken effectively micro-galvanic corrosion and increase corrosion resistance. After the extruded Mg-Li-Al-Zr alloy is immersed in NaCl solution, a dense and compact corrosion coating which consists mainly of Mg(OH)_2, LiOH, Li_2CO_3 and MgO forms on the surface.
Microstructure of Mg-10Li-5Al-0.02Zr alloy and the effects of extrusion on hydrogen and electrochemical corrosion behavior of Mg-Li-Al-Zr alloy in 3.5% NaCl(mass fraction) solution and the corrosion film structure were studied by X-ray diffractometry(XRD), electron probe micro-analyze(EPMA), scanning electron microscopy(SEM) and X-ray photoelectron spectroscopy(XPS). The results indicate that the Mg-Li-Al-Zr alloy after extrusion consists mainly of α-Mg, irregular AlLi, dispersed MgLi_2Al and β-Li phases. After extrusion, the structure of Mg-Li-Al-Zr alloy becomes more evenly, the grain size of Mg-Li-Al-Zr alloy refines, the number of second phases decreases. The average corrosion rates(PH) of Mg-Li-Al-Zr alloys before and after extrusion are(2.74±0.2) mm/a and(1.47±0.2) mm/a, respectively. A discontinuous banded structure forming along the extrusion direction and the uniform microstructure can weaken effectively micro-galvanic corrosion and increase corrosion resistance. After the extruded Mg-Li-Al-Zr alloy is immersed in NaCl solution, a dense and compact corrosion coating which consists mainly of Mg(OH)_2, LiOH, Li_2CO_3 and MgO forms on the surface.
引文
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[23]SHI Yin-chun,PENG Chao-qun,FENG Yan,WANG Ri-chu,WANG Nai-guang.Microstructure and electrochemical corrosion behavior of extruded Mg-Al-Pb-La alloy as anode for seawater-activated battery[J].Material&Design,2017,124:24-33.
[24]CAO Dian-xue,WU Lin,WANG Gui-ling,LüYan-zhuo.Electrochemical oxidation behavior of Mg-Li-Al-Ce-Zn and Mg-Li-Al-Ce-Zn-Mn in sodium chloride solution[J].Journal of Power Sources,2008,183(2):799-804.
[25]WANG Nai-guang,WANG Ri-chu,XIONG Wen-hui,ZHANG Jun-chang,FENG Yan.Electrochemical discharge performance of Mg-Al-Pb-Ce-Y alloy as anode for Mg-air battery[J].Journal of Materials Chemistry A,2016,4(22):8658-8668.
[26]SONG Y W,SHAN D Y,CHEN R S,HAN E H.Corrosion resistance of Mg-8.8Li alloy compared with AZ91[J].Corrosion Engineering Science&Technology,2014,46:719-723.
[27]WANG Nai-guang,WANG Ri-chu,PENG Chao-qun,PENGBing,FENG Yan,HU Cheng-wang.Discharge behaviour of Mg-Al-Pb and Mg-Al-Pb-In alloys as anodes for Mg-air battery[J].Electrochimica Acta,2014,149:193-205.
[28]LI C Q,XU D K,CHEN X B,WANG B J,WU R Z,HAN EH,BIRBILLS N.Composition and microstructure dependent corrosion behaviour of Mg-Li alloys[J].Electrochimica Acta,2017,260:55-64.
[29]SHI Yin-chun,PENG Chao-qun,FENG Yan,WANG Ri-chu,WANG Nai-guang.Enhancement of discharge properties of an extruded Mg-Al-Pb anode for seawater-activated battery by lanthanum addition[J].Journal of Alloys&Compounds.2017,721:392-404.
[30]ZENG Rong-chang,SUN Lu,ZHENG Yu-feng,CUIHong-zhi,HAN En-hou.Corrosion and characterisation of dual phase Mg-Li-Ca alloy in Hank’s solution:The influence of microstructural features[J].Corrosion Science,2014,79:69-82.
[2]LIU Xu-he,WU Rui-zhi,NIU Zhong-yi,ZHANG Jing-huai,ZHANG Mi-lin.Superplasticity at elevated temperature of an Mg-8%Li-2%Zn alloy[J].Journal of Alloys&Compounds,2012,541(1):372-375.
[3]DONG S L,IMAI T,LIM S W,KANETAKE N,SAITO N.Superplasticity evaluation in an extruded Mg-8.5Li alloy[J].Journal of Materials Science,2007,42(13):5296-5298.
[4]SUN Yue-hua,WANG Ri-chu,PENG Chao-qun,FENG Yan,YANG Ming.Corrosion behavior and surface treatment of superlight Mg-Li alloys[J].Transaction of Nonferrous Metal Society of China,2017,27(7):1455-1475.
[5]ZHANG Jing-huai,ZHANG Li,LENG Zhe,LIU Shu-juan,WU Rui-zhi,ZHANG Mi-lin.Experimental study on strengthening of Mg-Li alloy by introducing long-period stacking ordered structure[J].Scripta Materialia,2013,68(9):675-678.
[6]李瑞红,蒋斌,陈志军,潘复生.超轻Mg-Li-Al系变形镁合金挤压板材的组织及性能[J].中国有色金属学报,2016,26(1):31-36.LI Rui-hong,JIANG Bin,CHEN Zhi-jun,PAN Fu-sheng.Microstructure and mechanical properties of as-extruded ultra-light Mg-Li-Al sheet[J].The Chinese Journal of Nonferrous Metals,2016,26(1):31-36.
[7]FU H,GE B,XIN Y,WU R,FERNANDEZ C,HUANG J,PENG Q.Achieving high strength and ductility in magnesium alloys via densely hierarchical double contraction nanotwins[J].Nano Letters,2017,17(10):6117-6124.
[8]KIM Y H,SON H T.Effects of Li addition on microstructure and mechanical properties of Mg-6Al-2Sn-0.4Mn alloys[J].Transaction of Nonferrous Metal Society of China,2016,26(3):697-703.
[9]LIN M C,TSAI C Y,UAN J Y.Electrochemical behaviour and corrosion performance of Mg-Li-Al-Zn anodes with high Al composition[J].Corrosion Science,2009,51(10):2463-2472.
[10]XU Wan-qiang,BIRBILIS N,SHA Gang,WANG Yu,DANIELS J,YANG Xiao,FERRY MICHAEL.A highspecific-strength and corrosion-resistant magnesium alloy[J].Nature Materials,2015,14(12):1229-1235.
[11]WANG Nai-guang,WANG Ri-chu,FENG Yan,XIONGWen-hui,ZHANG Jun-chang,DENG Min.Discharge and corrosion behaviour of Mg-Li-Al-Ce-Y-Zn alloy as the anode for Mg-air battery[J].Corrosion Science,2016,112:3-24.
[12]董鹏,陈鼎,陈振华,章凯.新型Mg-8Li-5Al-5Ca合金的微观组织、力学及耐腐蚀性能[J].材料导报,2017,31(18):64-71.DONG Peng,CHEN Ding,CHEN Zhen-hua,ZHANG Kai.Microstructure,Mechanical Properties and Corrosion Resistance of a Novel Mg-8Li-5AI-5Ca Alloy[J].Materials Review,2017,31(18):64-71.
[13]SHI Zhi-ming;LIU Ming;ATRENS A.Measurement of the corrosion rate of magnesium alloys using Tafel extrapolation[J].Corrosion Science,2010,52(2):579-588.
[14]DONG Han-wu,WANG Li-dong,WU Yao-ming,WANGLi-min.Preparation and characterization of Mg-6Li and Mg-6Li-1Y alloys[J].Journal of Rare Earth,2011,29(7):645-649.
[15]WU R Z,QU Z K,ZHANG M L.Reviews on the influences of alloying elements on the microstructure and mechanical properties of Mg-Li base alloys[J].Reviews on Advanced Materials Science,2010,24(1):35-43.
[16]PAN Ying-cai,WU Guo-qing,CHENG Xu,ZHANGZong-ke,LI Mao-yuan,JI Su-dong,HUANG Zheng.Galvanic corrosion behaviour of carbon fibre reinforced polymer/magnesium alloys coupling[J].Corrosion Science,2015,98:672-677.
[17]PARDO A,MERINO M C,COY A E,VIEJO F,ARRABALR,FELIúS Jr.Influence of microstructure and composition on the corrosion behaviour of Mg/Al alloys in chloride media[J].Electrochimica Acta,2008,53(27):7890-7902.
[18]LIU Xiao-yan,WANG Zhao-peng,FU Bao-gang,LONGLiang,ZHANG Xi-liang,CUI Hao-xuan.Effects of Mg content on the mechanical properties and corrosion resistance of Al-Cu-Mg-Ag alloy[J].Journal of Alloys&Compounds,2016,685:209-215.
[19]SONG D,MA A B,JIANG J H,LIN P H,YANG D H,FANJ F.Corrosion behaviour of bulk ultra-fine grained AZ91Dmagnesium alloy fabricated by equal-channel angular pressing[J].Corrosion Science,2011,53(1):362-373.
[20]LI Jia-run,JIANG Quan-tong,SUN Hu-yuan,LI Yan-tao.Effect of heat treatment on corrosion behavior of AZ63magnesium alloy in 3.5 wt.%sodium chloride solution[J].Corrosion Science,2016,111:288-301.
[21]BARIL G,BLANC C,PéBèRE N.AC impedance spectroscopy in characterizing time-dependent corrosion of AZ91 and AM50 magnesium alloys characterization with respect to their microstructures[J].Journal of the Electrochemcal Society,2001,148(12):B489-B496.
[22]LIU Wen-juan,CAO Fa-he,CHEN An-na,CHANGLin-rong,ZHANG Jian-qing,CAO Chu-nan.Corrosion behaviour of AM60 magnesium alloys containing Ce or La under thin electrolyte layers.Part 1:Microstructural characterization and electrochemical behaviour[J].Corrosion Science,2010,52(2):627-638.
[23]SHI Yin-chun,PENG Chao-qun,FENG Yan,WANG Ri-chu,WANG Nai-guang.Microstructure and electrochemical corrosion behavior of extruded Mg-Al-Pb-La alloy as anode for seawater-activated battery[J].Material&Design,2017,124:24-33.
[24]CAO Dian-xue,WU Lin,WANG Gui-ling,LüYan-zhuo.Electrochemical oxidation behavior of Mg-Li-Al-Ce-Zn and Mg-Li-Al-Ce-Zn-Mn in sodium chloride solution[J].Journal of Power Sources,2008,183(2):799-804.
[25]WANG Nai-guang,WANG Ri-chu,XIONG Wen-hui,ZHANG Jun-chang,FENG Yan.Electrochemical discharge performance of Mg-Al-Pb-Ce-Y alloy as anode for Mg-air battery[J].Journal of Materials Chemistry A,2016,4(22):8658-8668.
[26]SONG Y W,SHAN D Y,CHEN R S,HAN E H.Corrosion resistance of Mg-8.8Li alloy compared with AZ91[J].Corrosion Engineering Science&Technology,2014,46:719-723.
[27]WANG Nai-guang,WANG Ri-chu,PENG Chao-qun,PENGBing,FENG Yan,HU Cheng-wang.Discharge behaviour of Mg-Al-Pb and Mg-Al-Pb-In alloys as anodes for Mg-air battery[J].Electrochimica Acta,2014,149:193-205.
[28]LI C Q,XU D K,CHEN X B,WANG B J,WU R Z,HAN EH,BIRBILLS N.Composition and microstructure dependent corrosion behaviour of Mg-Li alloys[J].Electrochimica Acta,2017,260:55-64.
[29]SHI Yin-chun,PENG Chao-qun,FENG Yan,WANG Ri-chu,WANG Nai-guang.Enhancement of discharge properties of an extruded Mg-Al-Pb anode for seawater-activated battery by lanthanum addition[J].Journal of Alloys&Compounds.2017,721:392-404.
[30]ZENG Rong-chang,SUN Lu,ZHENG Yu-feng,CUIHong-zhi,HAN En-hou.Corrosion and characterisation of dual phase Mg-Li-Ca alloy in Hank’s solution:The influence of microstructural features[J].Corrosion Science,2014,79:69-82.