Cl SO M AerMet CrMnSiMoVA 300M. (mass%) ÅC 0.40 Si 1.66 Mn 0.64 P S Cr 0.71 Ni 1.90 Mo 0.37 V Fe Ï Cr9 Ë Cr Ni Mo

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1 32 6 Û Å µ Ȳ Vol.32 No Ñ 12 Journal of Chinese Society for Corrosion and Protection Dec M Cr9 Ì ÓÕ ¹ Ä Đ 1 Þ 1 ÚØÛ 1 ß Ü 1 Ð 2 1. ² ˱ Ç ¹ 195 Ð : ¼ÈÒ Ë Ë± ± Å 3M Æ ± ÖÉ Ï (Ú Cr9 ) (H 2SO 4+Na 2SO 4) Ä ph Cl ÛÝ Ä 3M Cr9 E corr à ph ÔË ± ¾ R ct ÜÆ ÏÖ I corr ÔË ph Õ 3M Cr9 Ö Cl (H 2SO 4+Na 2SO 4) 3M Ð Cr9 Ò Cl ÆÆ ¹ Cr9 ¾ ÁÊÞË Ë Cr9 Cr Mo Ni ÔÕ Ì±Ý Æ Î 3M µ : 3M ± Ö Ë± ÞË Ô ½ : TG172.3 ³ËÁ : A Ѳ : Æ ĐÕ Å ĐÕ Í 138 MPa ½ Ë ĐÕ ĐÕ Ç Å ÞÇ ß Þ ½ß [1] Á ĐÕ Ë 3M AerMet CrMnSiMoVA 3M Á Ë ĐÕ Õ Ì À ³ ³ Ê Cl Ê Đ ³ Â Ç Ô± Ë Ü ³ Ì Ô±¹ ³ Đ È [2] Î Ð Ì ÔÆ ĐÕ³ ĐÕ É ³È Î 5 ² ²Ú ÉÊØ ØÊÁØ Ô Á Ë Cr Ni Co Mo W ¾ ÇÍË ³ ĐÕ ½ß Ì QuesTek» Đ ĐÕ ³ Ferrium S53 Ë Á ĐÕÉ 1985 MPa ÀÇÍÅ ÞÇ [3] Ð Í ĐÕ ¹ ( 3M AF ) À ³ Ô Ã Eliaz º ÈÅ : à : «¼² ³ Ù««6B) À Ó ³³ «( ) (FRF-TP-11- Ò : Å Õ 1985 Ò ±¼ ² Â Ï Ò : «lixiaogang99@263.net [4] 434 È ÎÈ À ³ ĐĐÔ Æ³Ô È ÍÔ ±Ô Ramadan [5] ĐÕ Cl SO 2 4 ph SCC ĐÕ ³ Đ ³ Ø Đ ± º À Ø Ð Đ Ú ĐÕ ³  ĐÕ ÝÊ ÝÊ Ê Ó Ë Ñ ÁÊ EIS Á Ê 3M Cr ĐÕ Ê Ã ph Ð Cl Ú ³ Å Ã 2 Ê ¼»»ÆÇ Đ ĐÕ 3M ĐÕÈ Î (Cr9)»Ç Ù 3M Ê (mass%) ÅC.4 Si 1.66 Mn.64 P.9 S.13 Cr.71 Ni 1.9 Mo.37 V.8 Fe Ï Cr9 Ë Cr Ni Mo Ë ³ ÜÊ (mass%) ÅC.19 Ni 5.3 Cr 9.4 Mo 1.4 Co V.24 W 1.4 S<.5 P<.2 Fe Ï Ð ß È Î ¾ÏÆ Î Î µ È ÉÎ Cr9 È Î 3M Ý [6]»Ç Princeton Applied Research» VMP3 Ê ¹ Ö Ê ÆË Ê

2 45 ³ Æ 32»Ç ÎÜ 3M Cr9 ¹ (1 mm 1 mm) ²Ö ¼ (SCE) ½ ÑÆ Ú SCE ¹ ÐÕ Ð 25 Ê.25(vs  EOC) 1.6 V (vs ½ E R ) Å 1mV/s EIS Ð ß µîü ³ Ä Þ EIS Ñ 1 mv Å Hz Ä»Ç ZSimpWin V3.2 Ú EIS ÐÁ»»Ç (H 2 SO 4 +Na 2 SO 4 ) ph Ð SO 2 4 ÔÕ.5 mol/l Cl Ú ³ à (H 2 SO 4 +Na 2 SO 4 ) Ô.5 mol/l NaCl 3 ÎÀ 3.1 Ç 1 ĐÕ 3M Cr9 ³ ph Ð (H 2 SO 4 +Na 2 SO 4 ) Ê Ä 1a Ý 3M ³ E corr.65 V E corr  ph ³.55 V Ø ph Ð 3M ½ À Ê ÊÚ ³ ÎÕ I corr  ph Û ² 12.5 ma/cm 2 ² I corr Ð 91.2 µa/cm 2 Û 2 Ñ ² I corr ÊÆÕ Û ² I corr 12.5 µa/cm 2 3M Ê À³ (H 2 SO 4 +Na 2 SO 4 ) Cr9 V ÌĐ Ã Ê Ø Đ» ÝÊ ( 1b).95 V Ì Cr9 Đ 2 à ÊĐÅ Đ Ã ÝÊ Ø Cr Ni ³ Þ ÝÊ Ê Ë (1.2 V ) Cr9 ³ źÊÊÔº ³ E corr  ph ʳ Ê ² ÝÊ Ê 19 µa/cm 2 Í ph Ð 2 ² ÝÊ Ð 8.9 µa/cm 2 1 Ñ ph ÐÑÝÊ Ê³Ê ( ²ÝÊ 6.91 µa/cm 2 ) 3.2 Ö Ê ÇÍ ³ Ê À Â Ë Ù ³ 2 3M ³ ph Ð (H 2 SO 4 +Na 2 SO 4 ) Ê Ú (H 2 SO 4 +Na 2 SO 4 ) 3M Nyquist É Å Å Ø ÊÚ ph 6 Ñ Đ Û Å Ø Å Å R ct Ë Å Ê Â ph Ð Û ( 2a) 3 Cr9 ³ ph (H 2 SO 4 +Na 2 SO 4 ) Ê Ú Æ ph ÐÞ Û Å Ø Đ Å Å ÂpH ÐÓ Ê ÓÊÅÄ ² Å Ê Đ Ä ² ÅÓÊ Å. (a) Fig.1 Polarization curves of 3M (a) and Cr9 in (H 2 SO 4 +Na 2 SO 4 ) solutions (a) Fig.2 Nyquist (a, b) and Bode (c) plots of 3M in (H 2 SO 4 +Na 2 SO 4 ) solutions lg ( Z / cm -2 ) (c) lg (f/ Hz)

3 6 Û Ä : 3M Cr9 ˱ 451 Ï Ø ½ ÅÐ ( 3a) Ø Ê Ã ²Ä 2b 3b bode Ý 3M Cr9 Ð Z ² ² ÐÓÊ Ä ph ÓÊ Ê³Ê Ø R ct ÊË 3.3 Cl 4 Cl Ú 3M Cr9 Ê Ã É Ý (H 2 SO 4 +Na 2 SO 4 ) Ô.5 mol/l NaCl Ä ³ ÞÐ 87 7 mv 3M I corr É 42 ÓÊ 279 µa/cm 2 Cr9 ÝÊĐÅ«± ½ ÀÉÝÊ Ê Ý Cl Ú ³ Ë Êà 3.4 ¾É Â»Ç Ð 3M Cr9 ³ ph Ð ³ Cl (H 2 SO 4 + Na 2 SO 4 ) ³ Ê ( 5) É Ý 3M H 2 SO (a) lg ( Z ) lg (f/ Hz) Fig.3 Nyquist (a) and Bode plots of Cr9 in (H 2 SO 4 +Na 2 SO 4 ) solutions (a) ph4+ Cl - ph4+.5m Cl ph4 Cl - ph4+.5m Cl Fig.4 Effect of Cl on polarization curves of 3M (a) and Cr9 in (H 2 SO 4 +Na 2 SO 4 ) solutions Fig.5 Morphologies of 3M (a c) and Cr9 (d f) after polarization in (H 2 SO 4 +Na 2 SO 4 ) solutions (a,d); (b,e); +.5 mol/l Cl (c, f)

4 452 ³ Æ 32 ³ Ê ³ ÃÃ Ø ( 5a)  ph Ð ³ Õ ½ 3M Đ ¹ Ø ³µ ³µ ËË Ð ³ Ø ( 5b) Ô Cl ³ Ê Õ Cl Ì µ ³µ Ê Óß µë ³ ØÙ ( 5c) Cr9 (H 2 SO 4 +Na 2 SO 4 ) Đ ³µ ³ Ê ßÞ Ü ³ Õ 3M ß (H 2 SO 4 +Na 2 SO 4 ) ³ Ê ( 5e) Í ph Ð 1 ² Đ º Ý ³µ ( 5d) Cl ³µ ËÆÓÔ Cl Å ³ ( 5f) 3.5 Í 6 3M Cr9 ³ ph Ð (H 2 SO 4 +Na 2 SO 4 ) Ê Ú Â 3M Đ Å Ç 6a ÐÁ [7] R s C dl R ct R o L 3M 5 Ê Ú Cr9 ÚÇ 6b ÐÁ Q Đ ß Stern-Geary»º Faraday ÐÃ Ý R ct Ð ¾ ³ Å Ê [8] R ct Ê Ñ ³ Å ³ R ct ÐÝ 7  ph ÐÓÊ 3M Cr9 R ct Ð ÓÊ ½ Ø ph ÐÚ (H 2 SO 4 +Na 2 SO 4 ) ³ ÅË Ð Ã Í ph ³ ÅÐ À O 2 «Ê À ݺ (1)Å O 2 +4H + +4e 2H 2 O (1) ÚÍ 3M ½ À Fe À ݺ (2)Å Fe Fe 2+ +2e (2) ÚÍ Cr9 V.95V ÝÊ Fe Cr Ni Mo Ê [9] ݺ (3 5) Í.95 V Ä Cr Ni ÝÊ Cr ÁÖ (Cr 6+ ) ³ CrO4 2 Ý º (6) 2Ni+O 2 2NiO (3) 4Cr+3O 2 2Cr 2 O 3 (4) 2Mo+3O 2 2MoO 3 (5) Cr 2 O 3 +5H 2 O 2CrO H + +e (6) Fig.6 Equivalent circuit models in (H 2 SO 4 +Na 2 SO 4 ) R ct 15 1 solutions (a) 3M,, ; other conditions 5 ph1 ph2 ph4 3 M Cr9 ph6 ph4+.5 mol/l Cl - Fig.7 Results of R ct for 3M and Cr9 in (H 2 SO 4 + Na 2 SO 4 ) solutions 3M Đ Å Û H + ØÖÈ Fe(I) Fe(II) Û H À Å(1) H + Đ Ê À Û (2) H Á H 2 (3) H 2 Ê H Û À ݺ (7 9) Fe+H + (FeH + ) ads (7) (FeH + ) ads +e (FeH) ads (8) (FeH) ads +H + +e Fe+H 2 (9) Û Fe(I) Fe(II) Ú ÀË ÇÊ Ç Ýº (1 11)Å Fe(I)+Fe Fe(I) ads +Fe(II) sol +2e (1) Fe(II)+Fe Fe(II) ads +Fe(II) sol +2e (11) Ø Û (FeH + ) ads (FeH) ads Fe(I) ads Fe(II) ads Î 3M (H 2 SO 4 +Na 2 SO 4 ) Đ Å [1] É 3M Cr9 Ê Ý Cr9 Ó Ô Cr Ni Mo Co Cr ÚË ³ ËÂÊ Ç Cr ÊØ Cr 2 O 3

5 6 Û Ä : 3M Cr9 ˱ 453 ÊØ Cr(OH) 3 Æ ÝÊ Cr 2 O 3 ÊØ Đ Ê Ì ³ [11,12] ÓÔ Cr ¼Ê ÝÊ Ð ÝÊÈ ÎÕ [9] Mo ³ ÇÚË ³ Ë Ð Ç Mo ÊÍÜǵ Þ Á ½ Î Ê È Î³ ±«[13] Mo «MoO 3 Cr Ê Ë ³ Ë Mo Û ÝÊ Õ ÝÊ Ì³ ÝÊ [7] Â Ë ³ Ô Mo Ë Ni Ô Ë ÍË ³ Ñ [14] ÇÊ Fe-2Cr Á Ô 65%Ni H 2 SO 4 ÍÓ ÓÔ² ³ Û ³ ËÆ Cr Mo Ni ÓÔË Cr9 ³ Ê ³ Ê Þ ³ ³ Á ³ ˳ ÚÍ Ã ³ à 5 Æ» (H 2 SO 4 +Na 2 SO 4 ) Ô.5 mol/l NaCl Cr9 ½ À ÉÝÊ Ê ³ ÎÕÓÊ 7 Ô NaCl Ä 3M Cr9 R ct Ð ÐÛ Cl ÐÔ ³ Å Ë Cl Î Ð ³ À Ä Ð ÝÈÒÐ [9] 4 À (1) 3M Cr9 ³  ph ÐÓÊ ½ R ct Û ³ ÎÕÓ Ê ph Ð Ð Ô 3M Cr9 (H 2 SO 4 +Na 2 SO 4 ) ³ (2) Õ Cl (H 2 SO 4 +Na 2 SO 4 ) 3M Đ ³ Cr9 ³ Cl Å ³ Đ Cr9 ½ ÀÉÝÊ Ê (3) Cr9 Cr Mo Ni ÓÔ Ë ĐÕ ³ Ü ³ Å Ð Í 3M [1] Malakondaian G, Srinivas M, Rama Rao P. Ultrahighstrength low-alloy steels with enhanced fracture toughness [J]. Prog. Mater. Sci., 1997, 42: [2] Figueroa D, Robinson M J. Hydrogen transport and embrittlement in 3M and AerMet1 ultra high strength steels [J]. Corros. Sci., 21, 52(5): [3] Liu M T, Liu J H, Zhong P. Research development of corrosion resistance of ultra-high strength steel [J]. Sci. Technol. Rev., 21, 28(9): (À, É, Ù. ² Õ [J]. ³ ÐÏ, 21, 28(9): ) [4] Eliaz N, Shachar A, Tal B, et al. Characteristics of hydrogen embrittlement, stress corrosion cracking and tempered martensite embrittlement in high-strength steels [J]. Eng. Fail. Anal., 22, 9(2): [5] Ramadan S, Gaillet L, Tessier C, et al. Detection of stress corrosion cracking of high-strength steel used in prestressed concrete structures by acoustic emission technique [J]. Appl. Surf. Sci., 28, 254: [6] Zhong J Y, Sun M, Liu D B, et al. Effects of chromium on corrosion and electrochemical behaviors of ultra high strength steels [J]. Int. J. Miner. Metall. Mater., 21, 17(3): [7] Pardo A, Merino M C, Coy A E, et al. Effect of Mo and Mn additions on the corrosion behaviour of AISI 34 and 316 stainless steels in H 2 SO 4 [J]. Corros. Sci., 28, 5(3): [8] Rehbach M S, Sluyter J H. In: Baord A J ed., Electroanalytical Chemistry [M]. New York: Marcel Dekker Inc., 197 [9] Xiao J M. Metallurgical Fundamentals of Stainless Steel [M]. Beijing: Metallurgical Industry Press, , ( ÒÍ. «³ÓÍ [M]. : «º, , ) [1] Hu Y B, Dong C F, Sun M, et al. Effects of solution ph and Cl on electrochemical behaviour of an Aermet1 ultra-high strength steel in acidic environments [J]. Corros. Sci., 211, 53(12): [11] Choi Y S, Shim J J, Kim J G. Corrosion behavior of low alloy steels containing Cr, Co and W in synthetic potable water [J]. Mater. Sci. Eng., 24, A385(1-2): [12] Keller P, Strehblow H H. XPS investigations of electrochemically formed passive layers on Fe/Cr-alloys in.5 M H 2 SO 4 [J]. Corros. Sci., 24, 46(8): [13] Jin H M, Wu X Q, Zheng Y G, et al. Effect of Mo content on the corrosion and erosion-corrosion of stainless steel in oil containing naphthenic acid [J]. Acta Metall. Sin., 22, 38(1): ( À,, Ü. Mo Ü ÍÀ «Å [J]. «³, 22, 38(1): ) [14] Staehle R W, Forty A J, Rooyen D. Fundamental Aspects of Stress Corrosion Cracking [M]. Ohio: The Ohio State University, 1967, 225

6 454 ³ Æ 32 ELECTROCHEMICAL BEHAVIOR OF 3M AND Cr9 STEEL IN ACIDIC ENVIRONMENTS SUN Min 1, XIAO Kui 1, DONG Chaofang 1, LI Xiaogang 1, ZHONG Ping 2 1. Corrosion and Protection Center, University of Science and Technology Beijing, Beijing 183; 2. Beijing Institute of Aeronautical Materials, Beijing 195 Abstract: The electrochemical behavior of 3M and a new kind of ultra high strength steel (Cr9 for short) in sulfate acidic environment, as well as the effects of ph and Cl concentration on the corrosion behavior were studied by potentiodynamic polarization curve, EIS, and metallographic microscope. The results showed that with increasing ph value, the corrosion potentials E corr of 3M and Cr9 shifted towards the positive direction, the charge-transfer resistances R ct increased, and the corrosion current densities i corr decreased. The (H 2 SO 4 +Na 2 SO 4 ) solution with decreasing ph value suppressed the corrosion rates of 3M and Cr9. In the chloride-free sulfate acidic solution, general corrosion on the 3M surface occurred, while on Cr9 surface pitting occurred. The addition of chloride ions induced the pittings and transformed the passivity of Cr9 into an active dissolution state. Cr9 steel contains more contents of Cr, Mo and Ni, and the elements enhanced the corrosion resistance in acidic solution and made a much lower corrosion rate compared with 3M. Key words: 3M, ultrahigh strength steel, acidic solution, electrochemistry, passivity ( ÝÙ 447 ) ZINC-NICKEL ALLOY ELECTROPLATING IN AN ALKALINE BATH LU Wenshan 1, XU Tianfeng 1, CHEN Yu 1, ZHANG Zhao 1, ZHANG Jianqing 1,2 1. Department of Chemistry, Zhejiang University, Hangzhou 3127; 2. State Key Laboratory for Corrosion and Protection, Institute of Metal Research, Chinese Academy of Science Shenyang 1116 Abstract: Zinc-nickel alloy coatings were electroplated from an alkaline electrolyte using direct current, the influences of principal technological parameters on the composition of zinc-nickel alloy coatings were studied using energy dispersive spectrometer (EDS). The results show that the content of nickel in Zn-Ni deposits kept between 11% and 13% and the co-deposition of zinc and nickel behaved anomalously. The microstructure of the optimized deposition was characterized by scanning transmission electron microscope (SEM), atomic force microscope(afm) and X-ray diffractometer(xrd), the results showed that the Zn-Ni deposits consisted mainly of the γ-phase(nizn 3 ) and the film was compact and fine-grained. Meanwhile, the Tafel plot measurements proved the coating had good corrosion resistance. Key words: zinc-nickel alloy, electroplating, alkaline, anomalous co-deposition, corrosion resistance