± Si Fe 0.42 Cu1.51 Mn 0.24 Mg 2.62 Zn. Al 2 (SO 4 ) 2 16H 2 O Å Õ [6] Al Ç SO 2 ÔÞ :

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1 Û 31 Û 6 ÀÀ² Vol.31 No Journal of Chnese Socety for Corroson and Protecton Dec. 011 Ý «SO ÆÂÓÜ± ¼ Ð ÇÍ 1 Ì È 1 ËÏÆ ÉÅ 1 Ä 1 Î Ê 1 1 (1. Á Ê ;. ¾Á ± Ë ¾ ) : Å SEM/EDX«Å Ö 7A0 Ò ² Ã SO Ó± ²Í ÖÆÞ µ ÊÕÐ ÃÓ Ã Æ ÕÐ Ó ÆÒ ²± ¾½ «Æ± Å Ó Þ Ö C=A t n ± ¾ÎÞÄ Æº½ Å É ÏÆÄ ½ Ó ÎÞ ± ¾²½Ó ÒÍ Ò ¾ ± Æ7A0 Ò ² 0.067% SO Ð ±ÓÕÐ Ã µ ÕÐÓ ¼ SO º Å Ñ : Ò ² Á¹Ú Đ : TG17.3 ½ ³ : A ½ Đ : « ÑÐÑ ± Å È ß ÂÌ ËÝÐ Ò½Î ÕÚ Þ ÉÅ Ì Õ Ñ Ð Ò Ü Â± º ÒÚ ±Ù Đ Ñ ± µ Ò Ì Ï± Í µ¹ SO ¹ Ò ÑÐ ± Ä ÒËÖ Đ Ú ßÔ Ñ ±µđ Ø Ò ÍÂ Ö Å ¹ [1 3] Svensson Õ [] Ó Ò SO Zn É µ SO Ò ËÖÒ µđß ØÒ» µđß ØÒ ß ±ÂµĐ Ò É ±ÙÒ µ Oesch Õ [5] Ñ SO µ Ò Đ ¹ ½ Ï ± Ñ SO ¹ µ ½± Al 3 (SO ) (OH) 5 9H O Ì Al (SO ) 16H O Å Õ [6] Al Ç SO Á/ ² Ò Đ Ì Õ Õ ÔÞ : : Á Â Ù³Ã ÎÂ Â ÙÍ Å ÎÃ 005DTA1000 Ì Ã Å : ÉÎ Æ 197 ½ Æ» Æ ³³Ú Ô³ Î Û Ã : ÉÎ E-mal: zhouhr 9@163.com ½±ÑÒ ¼ [7] µ Î SO Ñ 1060 ÐÑ ± A1 Ì 7A0 É µ Ò Ä ÅÌÚÎ ± SO Ñ ±Ò Õ [8] µ Î NaCl Ü Ì SO ß ± AZ91D É µ Ò ÄÅÌÚÎ Ë NaCl Ì SO ±Ò ¼ ±Ò Ì NaCl Ì SO Ñ ±ÒÉ µ Å ÒÊ ± SO Ô À º ÌÇºÕ» Ñ ± 7A0 SO ¹ Ò Ï± ¹ µ ÉÔ Â Ó Ò Ñ ± ¹ µ Ò Å Ì Ð ² Ö Ô ± 7A0 T6Å Â mass%å ± S Fe 0. Cu1.51 Mn 0. Mg.6 Zn 5.99 T Al Æ ± ÔÔ Ì Ñ ÄÔ ÔÔ ¾± 30 mm 0 mm.8 mm ßÅÈ Å 1500 # Í ßÈ Ì ² ²³ h Á Ä 0.1 mgå µ Ô» GB ±ÙÌ ÅÚ Ò Ò Ô Ï Ô Í ± SO Ô À ¹ µ Ä

2 6 ÈÍ Ö : ¼¹Ò ² ½ SO Ð Ó± ² 7 À SO µ SO ± 0.067% Ô µ ±»µ 0 Ô «± 8 h Øµ± 5 Ô «± 16 h ± 95% Ô Ç ± 0 d Ô «± h 6 h h 8 h 96 h 168 h 0 h 360 h 80 h ÐÂ Ð ÏÔÔ 3 Ä 1 ÍÝÌ ½ º Ô ± ÔÔ º 0.00 mol/l Na SO Ø ph ± 3.1Å Ô µ ±Óµ Ô Ç ± 70 h ÔÇ ± h 6 h h 8 h 96 h 168 h 0 h 360 h 80 h 70 h ÐÂÑ ± Ð Ë ÏÔÔ 3 Ä 1 ÍÝÌ ½ ÍÝ Ä ß (SEM) EDX ½ % SO Ø ÀÒÛ» 7A0 Ñ ± ÅµÌÇ 0.067% SO µ Ä «Ò 7A0 Ñ ± Moss loss /g/m % SO Wthout SO Tme /h Fg.1 Corroson loss of 7A0 alumnum alloy n pure atmosphere and 0.067% SO atmosphere Åµ Ô 80 h µđ Ø±¼ ½ ÄÝ ¼ Ð Ð Å» Ò Ä ¼ Õ 7A0 Ñ ± Ç 0.067% SO µ Ô ÄÝ Ô «Ò ÃÝµ Ñ ÄÝ Ï Ý Õ C = A t n (1) C g m Å± ĐÜ Ä t ± «hå A n Ò Ý Û 1Å Ý Â ± A=0.0 n=0.69 n ¹ 1 Ð Ä «Ò ¹ ÄÝ Ý n ± 0.69 Ð ÄÝ «Ò Í ºÈ Ý Ð 0.067% SO 7A0 Ñ ±Ò 7A0 Ñ ± Åµ Ô 80 h µ Đ Ø±¼ ½ 7A0 Ñ ±ÔÔ Ç 0.067% SO µ µđ ½Ò ÍÝ 7A0 Ñ ± µ h ÔÔµ ĐË ÆÞ h ÔÔµĐË Ò Æ ½ÌÇ ÒÒ ½ «Ò ½ÌÒ ½ÒÝ µå Ð 80 h ½ Ø± ÔÔµĐ ½Ã ÒÇ ¾ ÔÔµĐ Ì ½ ÔÔµĐÒÍÝ 3Å 7A0 Ñ ± Ä 96 h Ô µđå Ò Ä 3aÅ 80 h Ô µđå ÒÇ ½ Ú 3bÅ ËÌ± 7A0 Ñ ± Ç 0.067% SO µ µđ ½ ÂÇÅ Al S Ì O [5,6,9] 0.067% SO µ Í ÂÒ ½±¼Ò ÑÌ Ñß ½ Fg. SEM morphologes of 7A0 alumnum alloy n 0.067% SO atmosphere. (a) h, (b) h, (c) 96 h, (d) 168 h, (e) 0 h, (f) 80 h

$` n [ L y :. ` nd0 ). K 7A0 m X %"Y {T 0.00 mol/l Na SO -DZ;8 "X 1 ndzcq wb ph3.1 DtF[^. np JÆ 7A0 m 1 Xy B J % A=0.1 n=0.96 } 0.00 X %"Y { F. 70 h `[ L y : P.$ $)D n mol/l Na SO ph3.1 D t ` 7A0 m X %n $b $b[ly: ` n;8t%%dz;8 7A0 m X %"Y { F p 70 h ` ) _ t %0 $b A1 7A0 m X %" 0.00 mol/l Na SO ph3.$ $6 h `pp) SA T ^ z T zx r < X [N\z 5a z% N$bA1 [N\z%mX%) $ bd"\zt$ba1 6a h `pp) x 5SA nzx $b L T X $b A1 5b T 6b 96 h `pp) SAd^zX on$b A1 #% 7A0 mx%) d^zbujnzbl Fg.$

3 FF$b a_ 8 $8/ 31 "AHnw D Fg.3 SEM morphologes of 7A0 A1 alloy surface after elmnatng corroson products. (a) 96 h, (b) 80 h x " 0.00 mol/l Na SO ph3.1 D tf[^. ` n [ L y :. ` nd0 ). K 7A0 m X %"Y {T 0.00 mol/l Na SO -DZ;8 "X 1 ndzcq wb ph3.1 DtF[^. np JÆ 7A0 m 1 Xy B J % A=0.1 n=0.96 } 0.00 X %"Y { F. 70 h `[ L y : P. )D n mol/l Na SO ph3.1 D t ` 7A0 m X %n $b $b[ly: ` n;8t%%dz;8 7A0 m X %"Y { F p 70 h ` ) _ t %0 $b A1 7A0 m X %" 0.00 mol/l Na SO ph3.1 D tf $b 0 ` n) Uy G 5 j 7A0 mx%"dtf. 6 h `pp) SA T ^ z T zx r < X [N\z 5a z% N$bA1 [N\z%mX%) $ bd"\zt$ba1 6a h `pp) x 5SA nzx $b L T X $b A1 5b T 6b 96 h `pp) SAd^zX on$b A1 #% 7A0 mx%) d^zbujnzbl Fg. Corroson mass loss of 7A0 alumnum alloy n T$bA1 5c 0 h `pp) '%[N mol/l Na SO soluton mol/l Na SO ph mol/l Na SO 70 Pure water Mass loss /g m Tme / h Fg.5 Surface morphologes of 7A0 alumnum alloy n 0.00 mol/l Na SO soluton. (a) 6 h, (b) h, (c) 96 h, (d) 0 h, (e) 80 h, (f) 70 h

$70h `pp) $ba1,w $ba1 5e l 70 h `pp) x5uj` O Al S O T Cu X*C m X %" 0.00 mol/l Na SO ph3.1 D t _n$ba1> 5f T 6d OX$bA1F d^n : :& t $b$eky\ : FUJn$bA1%0ngmTh m{x1, H m X % t ja 7A0 m X %& F { $b 3.$ 3 h n { qu [Ly:KDZ) d )$bn v 3s N 9 In ) L 7 % 7A0 m X %" 0.00 mol/l Na SO M 1Q PA/ j d )- 91q ph3.

3 h n { qu [Ly:KDZ) d )$bn v 3s N 9 In ) L 7 % 7A0 m X %" 0.00 mol/l Na SO M 1Q PA/ j d )- 91q ph3.

4 PUBr : 0-nY&#1 SO l8go% X&~F<[g= 9 $b A1) $b A1n x )d 5d 80 LM 7A0 mx%" 0.00 mol/l Na SO ph3.1 h `p p) [N$b A1,v3) $ba1n x)d UJOX v ) UJ 0 n DtF[^. 70h `pp) $ba1,w $ba1 5e l 70 h `pp) x5uj` O Al S O T Cu X*C m X %" 0.00 mol/l Na SO ph3.1 D t _n$ba1> 5f T 6d OX$bA1F d^n : :& t $b$eky\ : FUJn$bA1%0ngmTh m{x1, H m X % t ja 7A0 m X %& F { $b 3.3 h n { qu [Ly:KDZ) d )$bn v 3s N 9 In ) L 7 % 7A0 m X %" 0.00 mol/l Na SO M 1Q PA/ j d )- 91q ph3.1 DtF$b`T6$bA1n) Uy 0 nb %u*srf< /, m X %" 6 s- 9 h p `p p) n $b z 7a 70 h p 7 Fn$bW% 7A0 mx%"/t) : `) n$bæ3 5~.eL SO ) p [^. py}o.p $b 7b ` 3 n $b Uy ~ d K X_p J 7A0 mx%" (d)p-n 7A0 m X %"0 $b $E 7 ; 7A0 m X % Qp J,W X y o p "Dt$EFr?n $b. $bz ~ e! QpnE;Z 7A0 mx%") $EF$b ).XT on; Z n ; l 1n0 7 } ; Z on; Z ) tu ; y $b v8? W p n 3 n=3nt \ n IM r \ dn$ 6! [5,6,9,10] (>B. (> # 3 [11] [1] Fg.6 SEM morphologes of 7A0 alumnum alloy n 0.00 mol/l Na SO soluton. (a) 6 h, (b) h, (c) 0 h, (d) 70 h Fg.7 SEM morphologes of 7A0 alumnum alloy surface after elmnatng corroson products. (a) 0 h, (b) 70 h

5 50 31 Ö Ï ¹Ê Ì ÐĐ «Ò ÁÅ ÖĐ ËÏ±Ò Å Ô Ý Ò ÎÎ ÄÅ Ü Ý X 0 = (X 0 (1), X 0 (),,X 0 ()); X 1 = (X 1 (1), X 1 (),,X 1 ()); X n = (X n (1), X n (),, X n ()) 1ÅÉ X 0 = ( X 0(1) X 0 (1), X 0() X 0 (1),, X 0() X 0 (1) ); X 1 = ( X 1(1) X 1 (1), X 1() X 1 (1),, X 1() X 1 (1) ); X n = ( X n(1) X n (1), X n() X n (1),, X n() X n (1) ) Å¾Ý 1 = X 0 () X 1 () = X 0 () X () n = X 0 () X n () 3Å¾ È È mn n X 0 () X () ; = 1,,,n mn mn X 0 () X () ; = 1,,, n max max X 0 () X () ; = 1,,, n max X 0 () X () ; = 1,,, n Å Ý ξ () = [mn 0.5 mn 0.5 max mn X 0 () X () + mn X 0 () X () ]/ [ X 0 () X () + max X 0 () X () ] 5Å γ = 1 n =1 ξ () γ ± X À X 0 Ò 6Å Ñ γ Ò ÈÊ γ Ð Á Ý 7A0 Ñ ± Ô ¹ Ô Ò ÄÝ «ÝÓ Ô Ò ÄÝ ± Ô ¹ Ô ÒÝ Ò «± Ì 1 Å Ó 0.067%SO µ Ô ÄÝ Ò «± h 96 h 0 h 80 hå º ÌÇº Ô ÄÝ Ò «± 8 h 168 h 360 h 70 hå Ô ¹ Ô Ó Ô ÄÝ Ð Æµ 1 µ 1 Ý 7A0 Ñ ± 0.067%SO µ «Ô Ò» 0.97Å ±» 0.00 mol/l Na SO ph3.1å ØÌ 0.0 mol/l NaHSO 3 ph6.1å Ø Ò ± 0.83 Ì 0.69 Â Đ 7A0 Ñ ± 0.067%SO µ «Ô Ò» Ô Â Ô Ò Ë 3. Ù µ 7A0 Ñ ±»Øµ«SO µ º Ô Çº ÝÐ Ò ĐØ± ÒĐ± Ú Ò ß ÑØ ¼ Â± ßÇÒ ßÌÑß µđì ÍÂ¼Ý ßÇ [13 16] 7A0 Ñ ±»Øµ«SO µ º Ô ÝÐÇº ÔÔµ Đ Ô Ø Ò¼ Ô Ñ ± ÒÄÅÌ Ú ØÅ¼»Øµ«SO µ SO µ Ö ß Ú Üß Ü SO Å ¹ÍÂ Table 1 Corroson loss lst and correlaton degree of 7A0 Al alloy n dfferent condtons Test condton Corroson loss lst g/m «Atmospherc test n X JC = 0.58Æ1.3Æ.9Æ.19«Jangjn staton Atmospherc test n X JC1 =.17Æ.8Æ8.3Æ15«0.067%SO atmosphere Immerson n 0.00 mol/l X JC =.93Æ16.01Æ31.79Æ69.«Na SO ph3.1«soluton Cyclc wet-dry mmerson X JC3 = 0.93Æ3.1Æ10.7Æ5.1«Test n 0.0 mol/l NaHSO 3 ph6.1«soluton Nate: R JC1 =0.97, R JC =0.83, R JC3 =0.69

6 6 ÈÍ Ö : ¼¹Ò ² ½ SO Ð Ó± ² 51 ßÍ ØÃ ßÒ Â ÄÅ± [9] SO + H O H SO 3 () H SO 3 H + + HSO 3 (3) HSO 3 + [O] HSO () HSO H+ + SO (5) Û Al Òß ph Ñ ±µđíâò Ò Ñ ß µđíâ ½ Ú Ã ± Al O 3 + 6H + Al H O (6) x(al 3+ ) + y(so ) + z(oh ) Al x (SO ) y (OH) z (7) 7A0 Ñ ± 0.0 mol/l NaHSO 3 Ø Çº µđíâò Al O 3 ½ ÇÅ ØØ Ì Ú Ã [9] ± HSO 3 + [O] HSO (8) HSO H+ + SO (9) x(al 3+ ) + y(so ) + z(oh ) Al x (SO ) y (OH) z (10) x(al 3+ ) + y(hso ) + z(oh ) Al x (SO ) y (OH) z (11) 7A0 Ñ ± 0.00 mol/l Na SO ph3.1å Ø º Ú Ë Ò ÄÅ¼ 7A0 Ñ ±»Øµ«SO µ ÌÇº ÄÅ± - - Ñ ± µ ÉÔ Ò ÄÅØ± Đ 7A0 Ñ ± 0.00 mol/l Na SO ph3.1å Ø º Ú Î «Ý ÄÝ» 7A0 Ñ ± ÃÂÔ Ò ÄÝ 7A0 Ñ ± ËÜ 3 Â SO Ô Ò 7A0 Ñ ±»Øµ«SO µ Ô Ò ÄÅØ± ÄÝ ³ Ò ÑØ ± Đ ± 0.97 ±» 7A0 Ñ ± 0.00 mol/l Na SO ph3.1å Ø Ô Ô Ò ÄÅÅ ± A0 Ñ ± 0.0 mol/l NaHSO 3 Ø Çº ÒÔ ¼ Ô Ò ÄÅØ± ÄÝ Ò Ñ 7A0 Ñ ± 0.0 mol/l NaHSO 3 Ø Çº Ò ÄÝ» ± 0.69 (1) 0 8 h 5 16 h 95% RHÅ 7A0 Ñ ± Ç 0.067% SO µ Ò ÄÝ Ô «Ý Õ C = A t n ½ÍÝ± ÖÞ ËÖ± ¼Ò ÑÌ Ñß ½ () 7A0 Ñ ± 0.00 mol/l Na SO ph3.1å Ø º 70 h ÄÝ «Ò Ý Õ C = A t n ½ÍÝ±¼ Ò ÖÇ µ ½±¼Ò ÑÌ Ñß ½ (3) Đ 7A0 Ñ ± 0.067% SO µ «ÒÔ Â Ô Ò» Ð ¾ [1] Neufeld A K, Cole I S, Bond A M, et al. The ntal mechansm of corroson of znc by sodum chlorde partcle deposton[j]. Corros. Sc., 00, : [] Oh S J, Coo D C, Townsend H E. Atmospherc corroson of dfferent steels n marne, rural and ndustral envronments[j]. Corros. Sc., 1999, 1: [3] Zhou H R, Ma J, L X G. Corroson behavor of 7A0 alumnum alloy deposted wth sodum chlorde n smulated envronment[j]. Chn. J. Nonferrous Met., 009, 19(5): (ÉÎ, ÛÅ, ÏÇ¹. ÀÝÔ Ô 7A0 Ó ³ Ñ ÁÔ³ ³. ÁÁ«Ç³Ú, 009, 19(5): ) [] Svensson J E, Johansson G. A laboratory study of the ntal stages of the atmospherc corroson of znc n the presence of NaCl, nfluence of SO and NO [J]. Corros. Sc., 1993, 3(5): [5] Oesch S, Faller M. Envronmental effects on materals: The effect of the ar pollutants SO, NO and O 3 on the corroson of copper, znc and alumnum. A short lterature survey and results of laboratory exposures [J]. Corros. Sc., 1997, 39(9): [6] Han W, Wang Z Y, Yu G C, et al. Corroson of alumnum n wet/dry envronment contanng SO [J]. Chn. J.Nonferrous Met.. 003, 13(): (Æ, ¾Õ, Á. Ó È SO Â/ ³Ñ ÁÔ³. ÁÁ«Ç³Ú, 003, 13(3):631-63) [7] Zhou H R, L X G, Dong C F. The corroson behavors of alumnum alloys n smulated SO pollute atmosphere [J]. J. Aeron. Mater., 008, 8(): 39-5 (ÉÎ, ÏÇ¹,. Ó ³ SO» Ñ ÁÔ³ ³ [J]. ÊÆ. 008, 8(): 39-5) [8] Ln C, L X G. Atmospherc corroson ntal stages of magnesum alloy n the presence of NaCI and SO [J]. J. Unv. Sc. Technol. Bejng, 00, 16(5): 5-58

7 5 31 (, ÏÇ¹. NaCl ÀÝÎ SO» ³Ê ³ ³Ô Â [J]. Â, 00, 16(5): 5-58) [9] Graedel T E. Corroson mechansms for alumnum exposed to the heat atmosphere [J]. J.Electrochem. Soc., 1989, 136(): 0c-1c [10] Zhou H R, L X G, Ma J. Dependence of the corroson behavor of alumnum alloy 7075 on the thn electrolyte layers [J]. Mater. Sc. Eng., 009, 16 B: 1-8 [11] Zhou H R, L X G, Dong C F. Corroson behavors of alumnum alloys after cyclc wet-dry mmerson test n 0.0 mol/l NaHSO 3 soluton [J]. J. Chn. Soc. Corros. Prot., 008, 8(6): (ÉÎ, ÏÇ¹, ÛÅ. Ó ³ NaHSO 3 ÙÁ É»³ Đ ³ [J]. ÁÁ³, 008: 8(6): ) [1] Zhou H R, Ma J, Lu Q K. Corroson study of alumnum alloys n Jangjn envronment [J]. Equp. Envron. Eng., 009, 6(3): 10-1 (ÉÎ, ÛÅ, Ð². Ó ³ Ñ ÁÔ³ ³. Ï Ñ Æ, 009, 6(3): 10-1) [13] LI J F, Zheng Z Q, Ren W D. Functon mechansm of secondary phase on localzed corroson of Al alloy[j]. Mater. Rev., 005, 19(): (Ï½,,. ÜÆ Ó ³ ³ ÁÔ Û [J]., 005, 19(): 81-83) [1] Buchhet R G, Grant R P, Hlavaa P F, et al. Local dssoluton phenomena assocated wth S phase(al CuMg) partcles n alumnum alloy 0-T3 [J]. J Electrochem. Soc., 1997, 1(8): [15] Buchhet R G, Martnez M A, Montes L P. Evdence for Cu on formaton by dssoluton and dealloyng the Al CuMg ntermetallc compound n rotatng rng-dsh collecton experments [J]. J Electrochem.Soc., 000, 17: [16] Lao C M, Olve J M, Gao M, et al. In-stu montorng of pttng corroson n alumnum alloy 0[J]. Corroson, 1998, 5: CORROSION BEHAVIORS AND RELATIVITY OF HIGH STRENGTH ALUMINUM ALLOY IN DIFFERENT SIMULATED SO ENVIRONMENT ZHOU Herong 1, MA Jan 1, LI Xaogang, JIE Ganxn 1, FENG Hao 1, WANG Jun, ZHAO Yue 1 1. Chna Natonal Electrc Apparatus Research Insttute, Guangzhou ;. Corroson and Protecton Center, Unversty of Scence and Technology Bejng, Bejng Abstract: The corroson behavors of hgh strength alumnum alloy 7A0 n three dfferent expermental condtons have been nvestgated by scannng electron mcroscope (SEM), energy dspersve X-ray detecton (EDX), Fourer transform nfrared(ftir) and mass loss method, and the relatvty has been analyged wth the result of Jangjn atmospherc envronment. The results show that the corroson product ncreases wth testng hours prolongng, and the mass loss of corroson product obeys the exponental rule as C = A t n. Surface observaton shows that corroson product s agglomerated and extended forth. The corroson products are made up of alumna, alumnum sulfate hydrate and alumnum chlorde. The smulaton results for the alumnum alloy 7A0 at cyclc wet-heat condtons (0,8 h; 5, 16 h; 95% RH) n the 0.067% SO polluted envronment had better correlaton wth Jangjn exposure result accordng to the mass loss data n all smulaton methods n the paper. Key words: alumnum alloys, SO envronment, mass loss method relatvty

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