022Cr25Ni7Mo4N双相不锈钢选择性腐蚀行为与两相组织的关系研究
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摘要
采用电化学测试、热力学计算以及SEM、AES和XPS分析等方法研究了022Cr25Ni7Mo4N双相不锈钢选择性腐蚀行为与两相组织的关系。结果表明:022Cr25Ni7Mo4N双相不锈钢阳极极化曲线具有明显的"活化-钝化-过钝化"三段特征;在活化向钝化转换区间,存在两个阳极活化峰并分别对应-236～-238 mV的γ相溶解电位E_h和-287～-294 mV的α相溶解电位E_l;022Cr25Ni7Mo4N钢具有更高的E_l电位、更低的E_h电位及更小的阳极活化电位差ΔE,这与该钢较小的两相PREN差值相关;增加Cr、Mo、N含量可同时提升实验用钢α、γ两相PREN值,25.4%Cr,4.8%Mo和0.28%N (质量分数)成分条件下,两相间PREN值均可实现平衡;实验钢钝化膜中Cr主要以Cr_2O_3氧化物存在,α相处钝化膜过渡区宽度较γ相处的更窄。
The relationship between the selective corrosion behavior and the microstructure of 022Cr25Ni7Mo4N duplex stainless steel was studied by means of electrochemical test, thermodynamic calculation, SEM, AES and XPS. The results show that the anodic polarization curve of test steel has obviously three stages, activation-passivation-transpassivation. In the conversion interval of activation to passivation, there exist two anode activation peak potentials, E_h=-236～-238 mV and E_l=-287～-294 mV,which may corresponds to the dissolution potential of γ-phase and α-phase respectively. 022Cr25Ni7Mo4N steel has a higher E_l potential, a lower E_h potential and a smaller anode activation potential difference ΔE, which is related to the smaller difference of pitting resistance equivalent number(ΔPREN) between α-phase and γ-phase of the steel. The increase of Cr, Mo and N content can simultaneously increase the PREN value of α-phase and γ-phase of the test steel, and it can reach the balance of PREN between the two phases for the steel composed of 25.4%Cr, 4.8%Mo and 0.28%N(mass fraction). In such case, the Cr in the passive film is mainly as the chromia Cr_2O_3, and the transition zone width of the passivation film on α-phase is narrower than that on γ-phase.
The relationship between the selective corrosion behavior and the microstructure of 022Cr25Ni7Mo4N duplex stainless steel was studied by means of electrochemical test, thermodynamic calculation, SEM, AES and XPS. The results show that the anodic polarization curve of test steel has obviously three stages, activation-passivation-transpassivation. In the conversion interval of activation to passivation, there exist two anode activation peak potentials, E_h=-236～-238 mV and E_l=-287～-294 mV,which may corresponds to the dissolution potential of γ-phase and α-phase respectively. 022Cr25Ni7Mo4N steel has a higher E_l potential, a lower E_h potential and a smaller anode activation potential difference ΔE, which is related to the smaller difference of pitting resistance equivalent number(ΔPREN) between α-phase and γ-phase of the steel. The increase of Cr, Mo and N content can simultaneously increase the PREN value of α-phase and γ-phase of the test steel, and it can reach the balance of PREN between the two phases for the steel composed of 25.4%Cr, 4.8%Mo and 0.28%N(mass fraction). In such case, the Cr in the passive film is mainly as the chromia Cr_2O_3, and the transition zone width of the passivation film on α-phase is narrower than that on γ-phase.
引文
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[2]Zhang Y N.Application analysis of 2507 duplex steel in urea equipment[J].Proc.Equip.Piping,2011,48(6):58(张亚宁.2507双相不锈钢在尿素设备中的应用分析[J].化工设备与管道,2011,48(6):58)
[3]Wu J.Duplex Stainless Steel[M].Beijing:Metallurgical Industry Press,1999:22(吴玖.双相不锈钢[M].北京:冶金工业出版社,1999:22)
[4]Wang R G,Min G Q,Zheng W L.Selective corrosion during stress corrosion cracking of 00Cr18Ni5Mo3Si duplex stainless steel[J].J.Chin.Soc.Corros.Prot.,1998,18:47(王荣光,闵国全,郑文龙.双相不锈钢在应力腐蚀开裂过程中的选择性腐蚀[J].中国腐蚀与防护学报,1998,18:47)
[5]Gao J,Jiang Y M,Deng B,et al.Investigation of selective corrosion resistance of aged lean duplex stainless steel 2101 by non-destructive electrochemical techniques[J].Electrochim.Acta,2009,54:5830
[6]Lu X,Ha S N,Ren S Z.Failure analysis on SAF2205 duplex stainless heat exchange pipe[J].Heat Treat.,2013,28(4):74(陆昕,哈胜男,任颂赞.SAF2205双相不锈钢换热管腐蚀失效分析[J].热处理,2013,28(4):74)
[7]Symniotis E.Galvanic effects on the active dissolution of duplex stainless steels[J].Corrosion,1990,46:2
[8]Fu Y,Lin C J,Luo Y X,et al.A study on the selective dissolution behavior of duplex stainless steel in systems containing nitric acid[J].J.Chin.Soc.Corros.Prot.,2004,24:272(付燕,林昌健,罗亦旋等.双相不锈钢在含硝酸体系中的优选腐蚀行为研究[J].中国腐蚀与防护学报,2004,24:272)
[9]Tsai W T,Tsai K M,Lin C J,et al.Selective corrosion in duplex stainless steel[J].Electrochemistry,2003,9(2):170
[10]Lo I H,Fu Y,Lin C J,et al.Effect of electrolyte composition on the active-to-passive transition behavior of 2205 duplex stainless steel in H2SO4/HCl solutions[J].Corros.Sci.,2006,48:696
[11]Leygraf C,Pan J,Femenia M.Microscopic corrosion studies of duplex stainless steels[J].Acta.Metall.Sin.(Engl.Lett.),2004,17(5):625
[12]Guo Q S,Zhao J B,Cheng X Q,et al.Galvanic effect between ferrite and austenite in 2205 duplex stainless steel[J].Corros.Prot.,2015,36:1119(郭秋实,赵晋斌,程学群等.2205双相不锈钢奥氏体铁素体两相间的电偶作用[J].腐蚀与防护,2015,36:1119)
[13]Tsai W T,Chen J R.Galvanic corrosion between the constituent phases in duplex stainless steel[J].Corros.Sci.,2007,49:3659
[14]Femenia M,Pan J,Laygraf C,et al.In situ study of selective dissolution of duplex stainless steel 2205 by electrochemical scanning tunnelling microscopy[J].Corros.Sci.,2001,43:1939
[15]Li H.Investigation on the microstructure evolution and corrosion behavior of duplex stainless steel[D].Xi'an:Xi'an University of Architecture and Technology,2015(李惠.双相不锈钢组织变化及腐蚀行为的研究[D].西安:西安建筑科技大学,2015)
[16]Li S J,Song Z G,Zheng W J,et al.Influence of N on microstructure,mechanical property and pitting corrosion resistance of00Cr25Ni7Mo3N[J].Mater.Rev.,2011,25(S1):520(李树健,宋志刚,郑文杰等.N对双相不锈钢00Cr25Ni7Mo3N组织、力学性能和耐点蚀性能的影响研究[J].材料导报,2011,25(S1):520)
[17]Zhang J X,Chen J,Cheng S S,et al.Growth mechanism of color passive film formed on stainless steel 304 by using A.V.passivation[J].J.Chin.Soc.Corros.Prot.,1999,19:167(张俊喜,陈健,程胜松等.不锈钢载波钝化着色膜的形成机理研究[J].中国腐蚀与防护学报,1999,19:167)
[18]Zhang T,He H,Zhao C Z.Carrier passivation treatment for duplex stainless steel[P].China Pat,CN200810064147.1,2008(张涛,何欢,赵成志.双相不锈钢的载波钝化处理方法[P].中国专利,CN200810064147.1,2008)
[19]Ramírez-Salgado J,Domínguez-Aguilar M A,Castro-Domínguez B,et al.Detection of secondary phases in duplex stainless steel by magnetic force microscopy and scanning Kelvin probe force microscopy[J].Mater.Charact.,2013,86:250
[20]Wu Z Z.Research on hot treatment procedure and hot plasticity of super duplex stainless steel 00Cr25Ni7Mo4N[D].Kunming:Kunming University of Science and Technology,2006(吴忠忠.超级双相不锈钢00Cr25Ni7Mo4N热处理工艺和热塑性研究[D].昆明:昆明理工大学,2006)
[21]Guo L Q,Li M,Shi X L,et al.Effect of annealing temperature on the corrosion behavior of duplex stainless steel studied by in situ techniques[J].Corros.Sci.,2011,53:3733