Al(99.95%) Al-10Sr Ñ Sr(99.5%)
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- Βηθζαθά Δυοβουνιώτης
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1 «3 Í «6 ± ²» Vol.3 No.6 01 Ä 1 Journal of Chinese Society for Corrosion and Protection Dec. 01 Sb Î Mg-5Al-Sr Õ Þ ÖËÆ Øº Æ º ºÜ µà Ì Ä Æ È À 155 : Û«º ±± µ Å Sb Mg-5Al-Sr Ò 3.5 mass% NaCl µ ±µá ³ Mg-5Al-Sr-xSb(x= ) Ò 3.5 mass% NaCl µ ±Û Ñ ± ±Ú Ð Õ τ SbSr Æ ß ÓßØ Ò ±Ò ¼¾ Al Sr ÁÍÊÑÒ ± «Mg-5Al-Sr Ò 0.3% Sb ¼ ÁÍ α-mg Ð Al Sr ±Ê ¼¾ÄØ Ò ± Ö À ± ¾ ±Ä Ò ±µáï Ê : Mg-5Al-Sr Sb ±µá Đ Ð : TG9.6 È Ò : A Ç : Ù«Mg-Al-Sr Đ Ñ Í Ê ¾ ¹ À ± ÀÅ À Î [1 13] AJ6(Mg-6Al-Sr) Ñ Â ÉÇ Ã 6 Æ [13,1] à ī² Ñ Ô Sb Mg- 5Al-Sr Ñ À Æ [15] Mg-5Al- Sr Ñ Ë» α-mg»½ ÜËË Al Sr «Ô Mg 9 Al 3 Sr (τ ) É Sb Ü Ñ É «Đ SbSr «Ô τ Æ Sb 0.3% Sb» ÀÌ α-mg ««Al Sr É µ»½ã Æ Sb Ñ SbSr º³»½ Al Sr Sb ÀÌ ¼Î Ñ ¼ Ý Ñ [16] Mg-Al-Sr ĐÑ À Õ Ø Ä«Mg-5Al-Sr Ñ ÀÅ Sb Mg-5Al-Sr Ñ 3.5 mass% NaCl À Æ Í ÛØ : Ô : Á Ç Đ (BE010103) ¾ : 1968 Å ¼ º, Æ ÒÑÓ Ë² Å : «zililiu@sohu.com ß Ï Ö ÐÅ Mg(99.95%» ) Al(99.95%) Al-10Sr Ñ Sr(99.5%) Sb Đ (99.9%) Ë «Ñ ¹É» ² 1 ȹ Ñ Ï 0.5%SF 6 CO Ñ ß ÄÅÆ ³ Ü min ܺ ÐÓ Ð 50 Ñ» É» Ñ Õ Ü Ñ µ Ð 0 mm 10 mm 3mm Ö É Ô Èµ Ü 3.5% NaCl 100 h 0 ßÜ 00 g/l CrO 3 19 g/l AgNO 3 Ê min Ý Ý Ô Ø Èµ ¹ Ñ É» µ «µ µ Þ Ñ Ï Ã ν Å ÐÅ ν = W 0 W t S 0 t (1) W 0 Ð Ö W t Ð ÜÝ Table 1 Chemical composition of experimental alloys (mass%) Alloy Al Sr Sb Mg 5 Bal Bal Bal Bal.
2 6 Ð : Sb Mg-5Al-Sr Ò ±µá 79 Ý S 0 Ð ² t Ð µ CH660A Æ ¹ÅÃ Ñ ÚÅ µ Solartron S 160 / Ê»Þ Á Solartron S 187 Æ ¹»ÞÁ Ñ Æ ¹ Û Åʹ½ Åà Р1 cm Åò º Ö Ü Ü Ä Ã Ð 3.5% NaCl 0»Þ NaCl Ý Ü Ë É «Æ ĐÅŹÆßÆ Ð ¾½Æ ÉÆ Ð Æ Æ ÐÅ ÃÆ ÅÃÆ ¹Æ ËÜÏ ÎÝ 80 mm ÚÅ ÅÆÕÆ Ã Ð 10 mv/s ÆÕ³ 1.8 V 0. V Æ ¹ ÅÆ Í ³ Ð 0.1 Hz 10 khz Æ 5 mv µ XJP-300 Á Ñ 3.5% NaCl À» Ü ³ 3 ÐÑ 3.1 ÝÜ Mg-5Al-Sr Ñ 3.5 wt% NaCl Ê 100 h Ü Ã 1 ȹ Å Ð ³ Mg-5Al-Sr Ñ Ã À» Sb Ü È Ñ Ã È Sb Ð 0.3% Ñ Ã À Ð 0.35 mg cm d 1 Mg-5Al-Sr Ñ ÀĐÐ Î Æ Sb Ñ Ã Sb Ð 0.6% Ñ Ã Ð 0.57mg cm d1 Song [17] à (0.5 mg cm d1 ) Þ Ñ ÏÊ À 3. Ú Ð» Sb Mg-5Al-Sr Ñ 3.5 NaCl ÚÅ Æ Å Þ ½ ÆÕ (E) Æ ½ (logi) ÌÅ ÎĐ Ñ ÚÅÏ Corrosion rate/ mg cm - d Fig.1 Corrosion rate of experimental alloys Á Tafel Tafel ÚÅÃÑ Å ĐÑ Æ ½ corr ÆÕ (E corr ) Å Æ (R p ) [18,19] ² ȹ ¹ ËØ ÆÕ E corr Þ Ó Þ ² Þ Ý Ó»ÀÖ Ã Ñ² Å Æ R p ¼² Æ Ã À ¹ ² «Æ ¹² Í Á ÖÍÏ ² Å Æ Þ À Þ Æ Ã υ Æ ½ corr Å [0] Å υ = M nf corr = corr M/n () υ Ð Ã g m h1 corr Ð Æ ½ µa cm M Ð Ö g mol 1 n в Æ Ý mol F Ð Å 968 C 6.8 A h ÂÉ Æ Ã υ Æ ½ corr É ÎĐ Í corr ز Æ Ã ² Å Ð Mg-5Al-Sr Ñ ÆÕÀ Å Æ À Mg-5Al- Sr-xSb Ñ ² ½ À Ê ½ Ó 3 Ð Sb Mg-5Al-Sr Ñ Æ ½ Æ À Ð Mg-5Al-Sr Ñ Æ ½ À Ð A cm Ñ Í Ê À à Sb Ü Ñ Tafel lg (/ A cm - ) Passive zone Pitting E/ V Fig. Polarization curves of experimental alloys Table Corrosion current density, corrosion potential and linear polarization resistance of experimental alloy Alloy corr/ A cm E corr/ V R p/ω cm
3 80 ß¹ 3Í ÚÅ Tafel ÚÅ Å ½Ð Í ² É ß ÖÍß Æ ¹ Í Ð Æ «Ü (Mg ) Ã Æ ÐÎ Ã Ù Æ Ü (Mg ) Ù ÏÆ Æ Æ Æ ÆÕ ± µ Ó Sb µñ Å Æ Æ ½ ² Ä ³ Ñ Ô Sb ÀÌ Î Mg-5Al-Sr Ñ À Þ Sb Ð 0.3% Ñ ÆÕ Mg-5Al-Sr Ñ «0.738 V 0.58 V 0.5 V 0.39 V 0.33 V ÀÆÕÙ «Ù ( ȹ) 0.58 V 0.5 V Ù Æ ² Ý É Î Æ Æ» Р0.5 V Å ÆÜ Í Ý Mg(OH) «Ð ºÃ [1] Æ Í ³ ¼ 0.39 V 0.33 V Ù ÖÍ É«Ñ Æ» Í ¾ 0.3% Sb Ü Ñ Æ ½ Mg-5Al-Sr Ñ «À Ð A cm Å Æ ¼Mg-5Al-Sr Ñ 3» Đ Sb Ð 0.3% Ñ Ê º À Æ Sb Ñ ÆÕ Å Æ Ì Æ ½ ÑÃ Ñ Ó À Sb Ð 1.0% Ñ ÆÕ Ð 1.09 V ß Mg-5Al-Sr Ñ 0.85 V Å Æ Æ ½» ÊºÊ Þ À 3.3 Ì a b» Ð Ñ 3.5% NaCl corr / ma cm Sb Content/ % Fig.3 Effects of Sb content on corrosion current density of experimental alloys Ô ÍÚÅ ÃÑ Ñ Æ Ð CDCÅ R(Q(R(CR)))(CR) Ñ Æ Ð CDCÅ R(Q(R(C((LR)(CR))))) 5 ȹ Ñ Bode ( 6) Å Ð Ñ Nyquist ÚÅÏ À» Í Í À Þ Êº ÉÔ ÊºÊ ÆÝ Ñ Ê «À «Í Í À Þ Í» «À Þ Makar [] Ä» Ñ Nyquist ÚÅ Í Þ Ã ÎĐ Nyquist ÚÅ»Þ µã ÚÑ Í Z m / k cm Z m / k cm (a) Z Re / k cm (b) Z Re / k cm Fig. Nyquist plots of experimental alloys. (a) experimental values; (b) fitted values Fig.5 Equivalent circuit of experimental alloys. (a),, ; (b)
4 6 Ð : Sb Mg-5Al-Sr Ò ±µá 81 Þ ÂÞ Ñ Ã ÇÞ Ñ ÇÞ Ñ Í Þ Â (r) Đ Ð r > r > r > r ʺ À Ð ± Í Þ ² É Æ Æ Í Åµ Æ Æ R t Õ»Ô² CPE Ø Æ Æ R t ² ¼ ÆÕÐ E corr Æ Í Æ Æ Æ Í ÈÍ R t Ñ Æ ÍÑ È ³ [9,0 3] Æ Æ Æ Æ C dl Ê Ê ¼ ² É½Û ½ ß Í ÝÜ Æ ² Û Æ ² Ð Æ Á Æ ²» ²» ¼ Ï Õ ÕÔ Í Õ»Ô² CPE Ú Æ Æ C dl ĐÃ Þ Y 0 n ¼ CPE À Z CPE =1/[Y 0 (jω) n ] 0 n 1 Z CPE Ð CPE Y 0 ¼ CPE ß ω Ð»Í n Ð CPE ¼ (ÜÎ Æ ² Í Æ»½ À ² ß Í Þ»¼ À Ø ¼ À Þ) Þ n» Ð CPE» Ú² Æ Warburg Æ Æ [] n Þ CPE Þ Æ ² Þ ² ÃÈ ² n Þ CPE Þ ² ² ÃÏÐ À Phase angle/ deg f/ Hz Fig.6 Bode plots of experimental alloys Þ [3] Í Þ» Ñ ² Í [3,5] Ü Ò Ý Ý Í Å Æ C f Æ R f Ø Í Þ Ñ ² Æ Ü Î Þ ² Þ Ü Þ È [6] ÂÉ Æ ¹ [3] Æ ² «Æ Æ E À² ˱ X µæ / Åß ²¹ÐÅ Y = jωc dl 1 ( F R ct X dx de )/[1jω/( X )] (3) X Y Ðß ω Ð»Í C dl ÐÆ Æ R ct ÐÆ Æ F Ð ÅÆ X в Ë ± X = dx/dt (3)» Í» ÀÜ»ØÙ Í» Þ ( F / X)( X/ E) >0 Æ ¹ Í» À Þ ÚÅ Ì Å Ð Ñ 3.5mass% NaCl ² Ñ ß É Å ² θ ز¹ Ñ Æ ² ˱ X Æ Æ ÆÕ E Ç µ (dθ/de) <0 ÉÔ ÙÐ ÆÆ ÆÕ E Æ Æ ß» µ θ Æ Æ Çµ ( F / θ) <0 À³ß ( F / θ)( X/ θ) >0 Ç Ñ Æ ¹ Í» À Þ ² 3 Ð Ñ ZSimp Win ŲÃÑ Æ R s Ð Æ R t ÐÆ Æ CPE Ð Õ»Ô² C f в Æ R f Ð ² Æ R L L» Ð Ñ ² Æ Ü Î Æ»Þ² 3 É Å Ð ÈÅÑ R s Õ Æ Í ÆÕ Å» Ñ R t R f Ñ Õ Í Î CPE C f ¼ Ñ Ê ½ 0.3%Sb ÀÌ n Table 3 Equivalent circuit parameters of alloy,, and Alloy R s/ω cm R t/ω cm CPE C f /10 3 F cm R f /Ω cm R L /Ω cm L/H cm Y 0 /10 6 Ω1 cm sn
5 #\3$h{- 3U = Mg-5Al-Sr m9 &7o m9 3$ ) XPS 6L AZ1 AZ501 AZ91 ( Mg-Al o BÆÆg Æ iæ6" D 7 5 m9& {: EQ" ad Al h O li G h BÆÆ au >' VCm9?3$( sd Mg h O li Al ` h O m$qf H B 1 Al O : 7> m9 {& #" Bl MgO : MgO 3$8"# H ThA&X$ 3. Zy o Mg(OH) : 7> m9 H&B b 7 l ((;m9 3.5% NaCl #(A D QKlw $Q ( : 3$8"#`d 6 #3$x 3$$ ' dmz} m9 i m9& Xr7S N9 (Vx; ( JFY3$ 3$v"l $ R.& 3$$ M d $Q Cl )! :} α-mg h! _7 R. ' # bf p ` " Z " # [ ( X r A3$Æq E q} Ja $Æ N 1s (1 ) lm9# ` 7! 1 O H k } V! F $ { 9 /l3$au#f $f m9 # $ q 9q EP& $Qh $ " l $h $ 1 /11lW} m9 E /Aa α-mg hfx$q Ksl$f HaU M,f7 Al Sr M k7 p τ EQ dmp Æ &Xi -&X m9 $ud k7 p τ m9 n&x H e H & $ 3.5% NaCl #(A D#.Gw h V z = 6&X Mg Mg e a3se # o" 6 =% h;m9 -&X Mg H O Mg OH H #` 7! > q bv m9 #F MgH H O Mg OH H ` 7 `BJY" $ $ qq &X Fy$Q Mg OH Mg(OH) m9 E /Aa α-mg,f7 Al Sr dmz} H Qh =V &Xi -& M 0 /1 ` 7 SbSr EQ dm P X bv r; 6 H TF H _ m9 $ud ` 7 SbSr " H e-hhtf H) D ph m9 # b Hjs ` `" $ VC b d Mg(OH) OH : $Q Mg(OH) m9 E /Aa α-mg 7 Al Sr M $Q m9&: 8!/)A z3$æq js ` 7 SbSr EQ dmp m9 E m9 $bæ " lp wwsd $Æq $ud js ` 7 SbSr 3$ { [ ` d" b 7e l"t( ;m9 Mg-5Al-Sr 3$ 36 h $' Hp{ Z} }m $fj ~ Q T m9& } ) 3$ (;m9 Mg-5Al-Sr-xSb $ 3.5% NaCl # [ (A D# z3$æq E d $Æq E " F m9#! (β ) 3$aU# m9& $QRb {K : Song Rb )K 8 3 p [1] p p [7] [7] Fig.7 Corrosion morphology of experimental alloys etching in 3.5% NaCl solution. (a) Mg-5Al-Sr, 1 h; (b) Mg-5Al-Sr-0.3Sb, 1 h; (c) Mg-5Al-Sr-0.6Sb, 1 h; (d) Mg-5Al-Sr-1.0Sb, 1h; (e) Mg-5Al-Sr, 36 h; (f) Mg-5Al-Sr-0.3Sb, 8 h
6 6 Ð : Sb Mg-5Al-Sr Ò ±µá 83 (1)»½ β Ø Ñ Al Sr ʺ½»½ Ñ ² «Ñ ² ² Ê Õ Ã ( ) ÉÐÑ ÅÆ α-mg»½ β À ĐÐ Đ ±» 7f Ð Ø Ñ Mg-5Al- Sr-0.3Sb 8 h ³ ÀÔß Ð Ð Al Sr Ö Í Þ² α-mg Ü»½ β ² É Ø [8] Ð Ñ β ² É ¼ ½Ò ph ³ ¼Û Å Â À ß ÊµĐÆ ½ È µ Ý«Ü Í Ñ ÀÌ Æ Í Ü (Mg ) Ã Þ Mg Ã Æ ÐÎ Ã Í ÐÇ Ã ² Ù Æ Æ ÆÕ ± É Æ ÎÜ ( Cl ) Ò Ý Ý α-mg ¾ Í Ð Æ È Ç Æ ² ¹² ³ Î Ñ À () ÖÓ β»½»¼ Ø Ñ τ Ñ Đ SbSr Û Å Í» ÃÐÞÒ² Î [9] «ÆÇ [30] ëʺ ÃÐ α-mg «Ñ Đ Þ ÏÒÞ Ñ ² ß Û ÆÞ «Î ² [31] µñ Ã Ì 5 Ñ (1) Ñ Ô Sb ÀÌÎ Mg-5Al-SrxSb(x= ) Ñ 3.5% NaCl À Sb Ð 0.3% Ñ ÀÀ Æ Sb Ñ Àº³ () 0.3%Sb Ü Ñ ½»½ Al Sr ² É ÀÌÕ ÆÑ Í Mg-5Al-Sr Ñ Ñ ÆÕ Æ ½ Ã Ñ ÀĐÐÎ É [1] Baril E, Labelle P, Pekguleryuz M O. Elevated temperature Mg-Al-Sr: Creep resistance, mechanical properties, and microstructure[j]. JOM., 003, 55(11): 3-39 [] L Espérance G, Plamondon P, Kunst M, et al. Characterization of intermetallics in Mg-Al-Sr AJ6 alloys[j]. ntermetallics. 010, 18(1): 1-7 [3] Hou J C, Guan S K, Ren C X, et al. Effect of small addition of strontium on microstructure and electrochemical performance of Mg-Mn sacrificial anode[j]. J. Chin. Soc. Corros. Prot., 006, 6(3): (Ú, Ï, ĐÅ. ƻР¼  [J]. ² ³ ¹Ð¼, 006, 6(3): ) [] Trojanov Z, Drozd Z, Luk P, et al. Mechanical properties of a squeeze cast Mg-Al-Sr alloy[j]. Adv. Mater. Sci. Eng., 008, 9(): [5] Aljarrah M, Parvez M A, Li J, et al. Microstructural characterization of Mg-Al-Sr alloys[j]. Sci. Technol. Adv. Mater., 007, 8(): 37-8 [6] Bai J, Sun Y S, Xue F, et al. Effect of extrusion on microstructures, and mechanical and creep properties of Mg-Al-Sr and Mg-Al-Sr-Ca alloys[j]. Scr. Mater., 006, 55(1): [7] Bai J, Sun Y S, Xue F, et al. nfluence of annealing on microstructures, mechanical and creep properties of Mg- Al-Sr alloy[j]. Mater. Sci. Technol., 006, (10): [8] Cao H B, Zhu J, Zhang C, et al. Experimental investigation and thermodynamic modelling of the Mg-Al-rich region of the Mg-Al-Sr system[j]. nt. J. Mater. Res., 006, 97(): -8 [9] Zhao P, Wang Q, Zhai C, et al. Tensile and compressive creep behavior of coarse-grained Mg-Al-Sr castings[j]. Mater. Sci. Forum., BeiJing: 006, 56-59: [10] Parvez M A, Medraj M, Essadiqi E, et al. Experimental study of the ternary magnesium-aluminium-strontium system[j]. J. Alloys Compd., 005, 0(1-): [11] Czerwinski F, Zielinska-Lipiec A. The microstructure evolution during semisolid molding of a creep-resistant Mg- 5Al-Sr alloy[j]. Acta Mater., 005, 53(1): [1] Pekguleryuz M O, BarilE,Labelle P, et al. Creep resistant Mg-Al-Sr alloys[j]. J. Adv. Mater., 003, 35(3): 3-38 [13] Pekguleryuz M O, Baril E. Development of creep resistant Mg-Al-Sr alloys[j]. JOM., 001: [1] Klüting M L C. The new BMW inline six-cylindercomposite Mg/Al crankcase[a]. MA 6nd Annual World Magnesium Conference[C]. Berlin, 005: [15] Zhu X C, Liu Z L, Zhou G B, et al. Effects of Sb addition on microstructure and properties of Mg-5Al-Sr alloy[j]. Mater. Sci. Technol., in accepted (¹,, µ. Sb Mg-5Al-Sr Ó Â [J]. ¼ ÆÆ, à ) [16] Yang Z, Li J P, Zhang J X, et al. Review on research and development of magnesium alloys[j]. Acta Metall. Sinica., 008, 1(5): [17] Song G, Atrens A, Dargusch M. nfluence of microstructure on the corrosion of diecast AZ91D[J]. Corros. Sci., 1998, 1(): 9-73 [18] Shi Z, Liu M, Atrens A. Measurement of the corrosion rate of magnesium alloys using Tafel extrapolation[j]. Corros. Sci., 010, 5():
7 8 ß¹ 3Í [19] Cao C N. Corrosion Theory[M]. Beijing: Chemical ndustry Press, 00 (. ³ ¼ Þ [M]. : ¼Æ, 00) [0] Zhang B H, Cong WB, Yang P. Electrochemical Corrosion and Protection of Metals [M]. Beijing: Chemical ndustry Press, 005 ( Ù, Ù, Ï. ¼ ³ ¹Ð [M]. : ¼Æ, 005) [1] Song G, Atrens A. Understanding magnesium corrosion: A framework for improved alloy performance[j]. Adv. Eng. Mater., 003, 5(1): [] Makar GL,KrugerJ,Joshi A.Advances in MagnesiumAlloys and Composites[M]. Pennsylvania: Metallurgical Society, 1988 [3] Cao C N, Zhang J Q. ntroduction to Electrochemical mpedance Spectroscopy [M]. Beijing: Science Press, 00 (, ±Õ. ¼ [M]. : ¼, 00) [] Liu L, Hu J M, Zhang J Q, et al. Evaluation of protectiveness of organic coatings by means of high-frequency ES measurement [J]. Corros. Sci. Prot. Technol., 010(): (, Ý, ±Õ. Î ¼ ¹ Ð Â ± [J]. ³¼ ¹Ð. 010(): 35-38) [5] Kouisni L, Azzi M, Dalard F, et al. Phosphate coatings on magnesium alloy AM60: Part : Electrochemical behaviour in borate buffer solution[j]. Surf. Coat. Technol., 005, 19(-3): 39-6 [6] Bessone J B, Salinas D R, Mayer C E, et al. An ES study of aluminium barrier-type oxide films formed in different media[j]. Electrochim. Acta, 199, 37(1): [7] Song G L, Andrej A, Wu X L, et al. Corrosion behaviour of AZ1, AZ501 and AZ91 in sodium chloride[j]. Corros. Sci., 1998, 0(10): [8] Frederick, P S. Corrosion and protection of magnesium[a]. 37th Annual World Conference on Magnesium[C]. New York, 1980: [9] Song Y, Shan D, Chen R, et al. Effect of second phases on the corrosion behaviour of wrought Mg-Zn-Y-Zr alloy[j]. Corros. Sci., 010, 5(5): [30] Shi F, Yu Y C, Guo X F, et al. Corrosion behavior of ascast Mg 68 Zn 8 Y alloy with -phase[j]. Trans. Nonferrous Met. Soc. China., 009, 19(5): [31] Rajan A, Naing A, W Z, et al. Evaluation of microstructural effects on corrosion behaviour of AZ91D magnesium alloy[j]. Corros. Sci., 000, (8): EFFECTS OF Sb ADDTON ON CORROSON PROPERTES OF Mg-5Al-Sr ALLOY LU Zili 1, ZHU Xiaochun 1, ZHOU Guibin 1, L Jian 1. College of Materials Science and Engineering, Nanjing University of Aeronautics and Astronautics, Nanjing 10016;. Jiangsu Favour Automotive New Stuff Sci-Tech Co., Ltd, Changshu 155 Abstract: Corrosion weight loss, polarization techniques, electrochemical impedance spectroscopy(es) and corrosion morphology were used to estimate the impact of Sb addition on corrosion properties of Mg-5Al-Sr alloys in 3.5% NaCl solution. Experimental results show that the initial corrosion types of Mg-5Al-Sr-xSb(x=0, 0.3, 0.6, 1.0) alloy in 3.5% NaCl solution is pitting corrosion. Pitting originated in massive ternary τ phase and granular SbSr phase. The larger amount and the bigger size of these phases corresponds to the poorer resistance. Mesh distribution Al Sr phase can become an effective barrierofcorrosion. Adding 0.3% Sb not only refines the α-mg matrix of Mg-5Al-Sr alloy, but also promotes the formation of Al Sr phase which distributed more in network. The corrosion potential of the alloy shifts positive obviously, the corrosion current density and corrosion rate reduces, thus, the corrosion resistance of the alloy is improved. Key words: Mg-5Al-Sr, Sb, corrosion property
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