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Journal of Chinese Society for Corrosion and Protection

Vo1 .27 No .6 Dec. 2007

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81 1

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circuit board, PCB )

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Fig.1 The galvanic potential ( a ) and anodic galvanic current density ( b ) as func~ionof exposure time of bimetallic
cell system, CuISn63-Pb37, exposed in the atmosphere ( 4 0

OC,

95% RH) for 38 days

Fig.2 SEM surface morphologies of the uncoupled Cu after different time exposure in atmosphere
RH) ( a ) 8 d , ( h ) 21 d

(4095,

95%

Fig.3 SEM w~fac.ernorpholog~es of the coupled Cu after d~ffrrrnt tune exposure

( a ) 4 rl, ( b ) 8 d, ( c ) 21 d

IU

atrnosphr~r (40 %, 9 5 % R H )

Fig.4 SEM surface morpholog~es of the coupled Sn63-Ph37 after different tlmr rxpoiurr In atrnosphe~r ( 4 0 O C , 9 5 % R H ) ( a ) 8 d , ( b ) 21 d

Fig.5 SEM sur-fa~ernorpholog~es of ( d ) thr touplrd 51163-PI137 i o l t l e ~ , (1)) thr couplrd Cu dnd ( c ) thr uncoupled Cu exposed for 38 days In atrno5phr1r ( 4 0 Y, 95% R H ) :

I~l~;f~ias~~~%jf;H~~60 Kt ,?B%A%Rf!k!&i+F ,@N@J% c u #% i$!ic$+b!JZi(EPB$B2?Lk&'i&, fi Sn63-Pb37 #%Z ~EKI$B2?B!%P0iBSE%Bf&~!J%CEi -?!?@fFI Cu %@Rf&FWjEm?BT%&&Egf$+ 38 mtr $2,ig Cu @f&&$@iEf,, Sn63-Ph37 t*%@$f& PI] CU $R Sn63-Pb37 2l'qtl'?J$iBBf&2kGF%3ZG
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4000 3000 2000 1000

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u / cm-' Fig.6 ET-IR spectra of corrosion films on the coupled Cu

during different exposure period in atmosphere (40

Or

2'0

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60

80

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Fig.7 XRD spectra of the coupled Cu sample surface
corrosion products after 38 days exposure in atmosphere ( 4 0 T , 95% R H )

'T, 95% RH)

38 d

( a ) 4 d , ( h ) 8 d , ( c ) 21 d , ( d )

u / cm" Fig.8 ET-IR spectra of corrosion films on the coupled

Sn63 -Pb37 during different exposure period in atmosphere ( 4 0 CT,, 95% R H ) ( a ) 4 d , ( b ) 8 d , ( c ) 21 d , ( d ) 38 d

26 / "
Fig.9 XRD of the coupled Sn63-Pb37 sample surface
corrosion products after 38 days exposure in atmosphere ( 4 0

CC, 9570 R H )

t&~~!?~F!IPll#fiH, Sn63-Pb37 &ab9IJ#ti? *Hj% &ikfiH@F!$U3!6, mzi89%rd#Hi9%+@?&@+ ~ j f l & U ~ ~ f f f & @ ? & ~ ~ ,Cu+ Lj'@$j&jj$$+~@@$f&~ OH- S$j$ @i$!h~, @%%@7kfBq& 0 2 @% pH C %$&%C U ( C ~ H )@si&#&Eii!??$5,Ejlkkih$%%C ~~ ~n63-~b37&mh9'iikfl$$1W@g%%@t&, %33!g ,%EE&% j7, %?@@ @&%ik!$~ pH ,@@ C02 &g%iH7k'k PbO + Pb2++ CO,?- + HzO - PbC0,.Pb(OH)2 . 8933?&BE+IP+7k@, &S,L1: ~0,'- CU(OH)> & 3 46 (2) 2+&E$%Y@F7kH@@B9@@P:%fl% CuCOl Cu(OH),, 8

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%i%&fig Sn63-Pb37 iZ@;i%$mE@H %IG&EfE@F%& FT-IR iSE!, &E3 'FE@iFJ BPI,?!2iff;k@iJ!llF4 Sn63-Pb37 %@i@t&7%7JB(l$$?iE %@lfi$, iE!E@5 38 d % , & 1388cm-' !&$J!i! C - h!lp!l(kE?j$!@, 3300 cm-' - 3600 cm-' &m O : L2W fi OH- %l!$%%%!~&?i, XRD fi$fi @it&8 d %g&@ 3 ( 9)$~I%~%%!,"%~% 2PbCO,.Ph(OHb, Hkk ,I%tMnfYjS n 6 3 - ~ h 3 7 # %5!3&09% i k 8 ~ F f r % ~ r f ~ I . p W ~ ~&E&%% 8 % ~ P p E , Sn02 I PbO- "-"', fE!@$$@DkR$l'd &@E,I$F Cu & P BR

@%s%
[ 1 ] Guttenplan J D , Hashimoto I. N. Co~~osion control for electrical
contarts in sul)marine ba~ellelectronic equipment Prrform., 1978, 18( 12): 49-55 [ 2 ] Sin1,lair J D. Co~laaionof electronics [J]. J. Elertrochem. 50c.. 1988. 135(3): 89C-95C [ i ] 1.i Q. Corrosion of electronic matr~ials [J]. Electron. Compon. Matrr., 1996, 15(6): 48-50

[ 9 ] Mansfrld F, Kenkel J V. Galvanic c,o~-rosion A alloys of 1 effect of area ratio [J]. Corros. Sci., 1975, 15:239-250

UI.

The

[ l o ] Xu J L , Li M Z. Research on elertrochemical monitoring of atmospheric corrosion [ J ] . J. Chin. Sor. Con-os. Prot.. 1987,7( 1 ): 60-65

[.I].

Mater.

(%f~~,~$~$$.~?%~k%ik~%~~!~@~6%%[J].~
p % $ k , 1987,7(1): 60-65)
[ I I ] Zakipour 5 , Lygraf C. Evaluation of laboratory tests to simulate
indoor corrosion of ele(.tric:al contact materials [J]. J. Electrochem. Soc.. 1986, 133(1): 21-30 [I21 Chen Z Y , Zakipour S , Persson D. The effects of' sodium cliloride particles on the atmospheric co~~osion pure copper of Corrosion, 2004, 60(5) :479-49 1 [ I 31 Dehiemmr C, .4mmeloo F, Sutter E M M. X-Ray photoen~ission investigation of the corrosion film formrd on a polished Cu-13Sn alloy in aerated NaCl solution [J]. Appl. Surf. Sci.. 2001, 174: 55-61 [I41 Ryrk I D, Birzen E V. Study of tin corrosion: the influence of alloying elements [ J ] . J. Cultural Heritage, 2004. 5: 189-195 [J]

(+E.&3$A#4~J%i&[~].$-f-Zl+-tjtd$4,1996,15(6) :4850) [ 4 ] .4astmp T, Wadsak M, Shreiner M. Experimental in situ studies to of copper rxp(~srtl humidifird air [J j. Corros. Sci., 20W, 42: 957-967 [ 5 ] Shin B I., Young R Y , Ja Y J. Electrochrmical migration characteristics ot rutectir SnPb solder alloy in printed cin,nit I~oard[ J ] . Thin Solid Films. 2006. 504: 294
-

297

[6] Manning M I. Atmospheric rorrosion issues today [ J ] . Industrial Con-cis., 1989, 7(8): 5-9 [ 7 ] Mattsson E. Corrosion: an electrochemical problem [J]. Chem. Technol.. 1985. 4:234-243 [ 8 ] Cao C N. Electrochemical Corrosion Tliroly [MI. Beijing: Chemical Industrv Press. 2004

[ 15j 1.u Y K. Thermodynan~irsof surface corrosion of polid pure lead,

tin ant1 thrir alloy [.I]. J. Univ. Sci. Technol. Beijing, 1989, 11 ( 2 ) : 167-172

(g7kS. El&% 3%R ~ + & & ~ % ~ % ~ I Y [ S ] . ~ L ; C ?

ELECTROCHEMICAL CORROSION BEHAVIORS OF THE GALVANIC COUPLE CuISn63-Pb37 IN SIMULATED ATMOSPHERE

QIU Ping, Y AN Chuanwei , WANG Fuhui
(State Key Laboratory for Corrosion and Protection, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 1 10016)

Abstract: The CuISn63-Pb37 galvanic couple appeared in most electronic devices. This paper was to investigate
the corrosion characteristics and mechanisms of this couple, condition at 40 which was exposed in the typically simulated air

T with 95% RH. The in-situ

electrochemical information of the couple have been performed with the Cu acted as anode and the Sn63-Pb37 acted

related zero resistance ampere techniques under thin moisture film. According to the time dependent features of galvanic potential and anodic galvanic current density results, as cathode during exposure. The gradually formed corrosion products, which were detected by FT-IR and XRD, restrained the anodic polarization behavior occurring on Cu surface. The hydrolyzed CO, on the Sn63-Pb37 surface induced the breakdown of Pb oxides formed in air naturally, which was confirmed from the SEM surface morphologies. Despite of the exact corrosion rates not obtained from the galvanic current density data, the changing trend was valuable for estimating the atmospheric corrosion behavior of the CuISn63-Pb37 couple.

Key words: galvanic corrosion, Cu , Sn63-Ph37 solder