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Pitting and crevice corrosion of A1 alloys and Al-based metal Matrix Composites can be det ect ed by characteristic changes of the I mpedance spectra in the low frequency region. Chemical passivation process provides a valuable alternative to chromate conversion coatings.
Pitting and crevice corrosion of A1 alloys and Al-based metal Matrix Composites can be det ect ed by characteristic changes of the I mpedance spectra in the low frequency region. Chemical passivation process provides a valuable alternative to chromate conversion coatings.
Pitting and crevice corrosion of A1 alloys and Al-based metal Matrix Composites can be det ect ed by characteristic changes of the I mpedance spectra in the low frequency region. Chemical passivation process provides a valuable alternative to chromate conversion coatings.
F . M a n s f e l d , * S. L i n , S. K i m , * a n d H . S h i h * Corrosion and Envi r onment al Ef f ect s Laborat ory, Depar t ment of Mat eri al s Sci ence and Engi neeri ng, Uni versi t y of Sout hern Cal i f orni a, Los Angel es, Cal i f orni a 90089-0241 ABSTRACT Pitting and crevice corrosion of A1 alloys and Al-based metal mat ri x composi t es can be det ect ed by characteristic changes of the i mpedance spectra in the low frequency region. A pitting model has been devel oped whi ch is in agreement with the experi ment al data. A fitting procedure has been used to analyze a large amount of data whi ch have been obtained for as-received samples and samples whi ch had been passivated in CeC13 solutions. This chemical passivation process pro- duces surfaces whi ch are very resistant to localized corrosion. The chemical passivation process provides a valuable alter- native to chromat e conversion coatings. A16061, A1/SiC, and A1/graphite whi ch had been passivated in CeC13 for one week did not pit in 0.5N NaC1 for at least one month. El ect rochemi cal i mpedance spect roscopy (EIS) is a conveni ent tool for moni t ori ng of the passivation and the corrosion processes. The application of electrochemical i mpedance spectros- copy (EIS) as a new tool in corrosion research has resulted in a wealth of information concerni ng met hods of corro- sion protection whi ch were difficult to study with tradi- tional dc techniques. This includes corrosion prot ect i on by conversi on coatings (1), pol ymer coatings, and anodic films (2). EIS has also provi ded information concerni ng corrosion prot ect i on by inhibitors (3), a subject whi ch has been discussed more recently in connect i on with a new model of corroding surfaces whi ch takes into account the i nhomogenei t i es of most real surfaces (4). In this paper it will be demonst rat ed that EIS is also useful for det ect i on and moni t ori ng of localized corrosion phenomena. The corrosion behavior of A1 alloys and Al-based metal mat ri x composi t es in aerated 0.5N NaC1 will serve to illustrate this concept (5). It will be shown that chemical passi vat i on--a process whi ch consists of i mmersi on in CeC13 sol ut i ons-- produces surfaces which possess excel l ent resistance to localized corrosion (5-7). EIS has been used to moni t or the passivation process and will be used in the future to deter- mi ne the opt i mum passivation parameters. Recordi ng of EIS data during the corrosion test allows cont i nuous mon- itoring of the parameters whi ch characterize the properties of t he surface and their changes as localized corrosion occurs. In order to describe t he events whi ch occur on a cor- rodi ng surface before and after localized corrosion has been observed, the model shown in Fig. 1 has been de- veloped. This model is in agreement with a large number of EIS data which have been collected by the authors for A1 alloys and Al-based M1VICs (5-7). The parameters of this model are defined as follows: R, is the solution resistance, Rp is the polarization resistance of the passive surface, and Cp is the correspondi ng capacitance. Rpit is the polarization resistance of the pitted area and Cpit is its capacitance. F is the area fraction of the pitted surface (0 =<F =<1). W de- scribes the transmission line behavior which is observed at the lowest frequencies when pitting occurs and is ex- pressed as W = K(j~)n/F, where n and K are constants. A fitting procedure has been devel oped for the analysis of experi ment al i mpedance data whi ch is described else- where (8). Impedance spectra whi ch correspond to F = 0 and F = 0.005 are shown in Fig. 2. Even for this very small area at whi ch pitting is assumed to occur, very significant changes in the EIS data are observed. The pronounced in- crease of the capacitance Ct = Cp ( 1- F) + rcpi t , the change in the frequency dependence of the i mpedance at the lowest frequencies and the occurrence of a low fre- quency maxi mum of the phase angle are characteristic of t he pitting process. Hi nt on et al. (9-12) have used rare earth metal chlorides as inhibitors for A1 alloys in NaC1. It was assumed that the surface films formed in solutions such as 0.1M NaC1 and *Electrochemical Society Active Member. 1000 ppm of CeC13 reduce the rate of the oxygen reduct i on reactior L t hereby shifting the corrosion potential in the negat i ve direction, while the pitting potential remai ned unchanged. In the present approach, surface modification is achieved by i mmersi on in CeC13 for seven days or longer. The corrosion resistance of the resulting surface films is t hen tested by i mmersi on in 0.5N NaC1. The CeC13 is t herefore not used as an inhibitor, but as a subst ance whi ch forms a conversi on coating in the A1 alloy. Passiva- tion in CeC13 produced very corrosion resistant surfaces for most materials studied. As a result the i mpedance was very high and did not show a dc limit at the lowest fre- quenci es measured (usually 1-10 mHz). For these cases, where F = 0, a new fitting procedure was devel oped (13) whi ch allows det ermi nat i on of Rp despite the fact that the experi ment al data show mainly capacitive behavior. For cases where a dc limit of the i mpedance was observed in t he measured frequency range and localized corrosion did not occur, the integration t echni que (14) was used. E x p e r i m e n t a l R e s u l t s a n d D i s c u s s i o n The materials studied were AI 7075 in the T6 and the T73 condition, A1 6061, A1 6061/SIC, and A1 6061/graphite (A1/Gr). The A1/SiC MMC (DWA Composi t e Specialties) cont ai ned 25 vol ume percent (v/o) of 10 I~m SiC particu- lates whi ch were mi xed with A1 6061 powder and pro- cessed with an ext rusi on method. The AEGr MMC (DWA) cont ai ned 55 v/o of P 100 graphite fibers with eight al- t ernat i ng layers of graphite and A1 6061 and was clad with an A1 6061 face sheet of 50 ~m thickness. Surfaces were degreased, alkaline cleaned and deoxidized in a chro- mat e HNO3 bath (deoxidizer 17, Amchem) before exposure to the test solution. After exposure to CeC13, the samples R s 1 .... ] R p / [ 1 - F ] R p i t W F O ~ F ~< 1 , W----'(K/F)(Jr n Fig. 1. M o d e l for the impedance of the pitting process on AI-based materials. 78 J. El ec t r oc hem. Soc. , Vol. 137, No. 1, January 1990 9 The Electrochemical Society, Inc. ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 155.69.4.4 Downloaded on 2014-08-11 to IP J. E l e c t r o c h e m . So c . , Vol . 137, No. 1, Januar y 1990 9 T h e E l e c t r o c h e m i c a l Society, Inc. 79 ' l 5 5 N 3 i O 3 - 2 - 1 0 1 2 3 4 L o g f ( f i n H z ) 90 75 45 m t 5 0 F i g . 2 . S i m u l a t e d s p e c t r a f o r F = 0 ( c u r v e 1 ) a n d F = 5 - 1 0 - 3 ( c u r v e 2 ) w h e r e Rp = 5 104~),, Cp = 2 0 0 t~F, R , = 3 . 0 ~ , Rpi t = 2 . 5 , 0 , , C p i t 0 . 0 8 F , K = 2 . 5 ~ ( r a d / s ) - " , n = - 0 . 2 5 . 6 90 5 9 75 "~ 1 2 2 4 6 o ~ 3 4 5 ~ o, 2 3 o ~ m i 15 o o - 2 - 1 0 1 2 3 4 L o g f ( f i n HZ) F i g . 4 . C o m p u t e r f i t o f e x p e r i m e n t a l d a t a . 1 , A I 7 0 7 5 - T 6 a f t e r 2 h i n 0 . 5 N N a C I , p o s s i v a t i o n f o r o n e w e e k i n ] 0 0 0 ppm C e C I s , A = 2 0 cm2; 2 , f i t d a t a R , = 2 . 9 ~ , Rp = 1 6 3 ~ , C p = 1 6 2 ~ F , c~ = 0 . 9 5 . we r e r i n s e d s e v e r a l t i me s wi t h d e i o n i z e d wa t e r b e f o r e i m- me r s i o n i n NaC1. S a mp l e s we r e e x p o s e d h o r i z o n t a l l y a n d t h e t e s t cel l wa s c l a mp e d o n t h e s u r f a c e u s i n g a n o- r i ng as t h e seal . I n t h i s ma n n e r n o e d g e e f f e c t s oc c ur . Th e c o r r o s i o n b e h a v i o r d u r i n g e x p o s u r e t o CeC13 or NaC1 wa s mo n i t o r e d u s i n g EI S. I n mo s t t e s t s t h e s a mp l e wa s f i r s t i mme r s e d i n 1000 p p m CeC13 f or o n e we e k a n d t h e n t r a n s f e r r e d t o 0. 5N NaC1 ( o p e n t o ai r). Th e s e r e s u l t s we r e c o mp a r e d wi t h EI S d a t a f or s a mp l e s wh i c h we r e e x- p o s e d t o NaC1 wi t h o u t t h e c h e mi c a l p a s s i v a t i o n t r e a t me n t i n CeC13. T h e e x p o s e d a r e a of t h e t e s t e l e c t r o d e wa s 20 c m 2. Th e i mp e d a n c e s p e c t r a we r e o b t a i n e d a t t h e c o r r o s i o n po- t e nt i a l , E . . . . A s a t u r a t e d c a l o me l e l e c t r o d e ( SCE) wa s u s e d as t h e r e f e r e n c e e l e c t r o d e . I t wa s c o u p l e d c a p a c i t i v e l y t o a P t wi r e t o r e d u c e t h e p h a s e s h i f t a t h i g h f r e q u e n c i e s (15). Th e me a s u r e me n t s we r e c a r r i e d o u t wi t h a S o l a r t r o n Mo d e l 1250 f r e q u e n c y r e s p o n s e a na l yz e r a n d a Mo d e l 1286 p o t e n t i o s t a t . Th e a p p l i e d ac s i g n a l wa s 10 mV. Th e s p e c t r a we r e o b t a i n e d i n a t l e a s t t wo p a r t s i n o r d e r t o a c h i e v e ma x - i mu m s e n s i t i v i t y a t al l f r e q u e n c i e s . Us u a l l y t h e c u r r e n t me a s u r i n g r e s i s t o r wa s c h a n g e d a t 1 Hz t o a v a l u e wh i c h wo u l d ma t c h t h e i mp e d a n c e e x p e c t e d i n t h e l o w f r e- q u e n c y r a n g e . F o r t h e a n a l y s i s of t h e EI S d a t a t h e l o w f r e- q u e n c y r e g i o n c o n t a i n s v e r y i mp o r t a n t i n f o r ma t i o n s i n c e b o t h t h e p o l a r i z a t i o n r e s i s t a n c e a n d / o r t h e i mp e d a n c e el e- me n t s wh i c h a r e d u e t o p i t t i n g h a v e t o b e e x t r a c t e d f r o m t h e s e da t a . F i g u r e 3 s h o ws a t y p i c a l r e s u l t o b t a i n e d f or a s - r e c e i v e d A1 6061 f or wh i c h s o me p i t s h a d a l r e a d y i n i t i a t e d a f t e r 24h e x p o s u r e t o 0. 5N NaC1. Al s o s h o wn i n Fi g. 3 a r e t h e r e s u l t s of t h e c o mp u t e r fi t a n d a s i mu l a t i o n of t h e i mp e d a n c e d a t a i n t h e v e r y l o w f r e q u e n c y r a n g e t o t h e d c l i mi t o f t h e i m- p e d a n c e . Th i s l i mi t o c c u r s o n l y at 10 -6 Hz a n d i s t h e r e f o r e 6 . 90 b e y o n d t h e r a n g e o f t h e i n s t r u me n t a t i o n a n d r e a l i s t i c t i me s f or t h e me a s u r e me n t . F i g u r e 3 al s o s h o ws wh y t h e Kr a me r s - Kr o n i g (K-K) r e l a t i o n s c a n n o t b e u s e d f or t h e val - i d a t i o n of t h i s t y p e of d a t a i n t h e f r e q u e n c y r e g i o n wh i c h i s d o mi n a t e d b y t h e t r a n s mi s s i o n l i n e e l e me n t (16, 17). S i mu - l a t i o n s u s i n g t h e mo d e l i n Fi g. 1 h a v e s h o wn t h a t f or ex- p e r i me n t a l d a t a wi t h a l o w- f r e q u e n c y l i mi t of 10 -3 Hz a g r e e me n t wi t h t h e K- K t r a n s f o r ms wi l l o c c u r o n l y f or f r e- q u e n c i e s e x c e e d i n g a p p r o x i ma t e l y 10 -~ Hz. F o r t h i s r ea- s on, t h e K- K t r a n s f o r ms c a n n o t b e u s e d i n t h e p r e s e n t c a s e t o c h e c k t h e v a l i d i t y of t h e e p x e r i me n t a l d a t a i n t h e l ow- f r e q u e n c y r a n g e wh i c h i s d o mi n a t e d b y t h e p i t t i n g p r o c e s s . F i g u r e 4 s h o ws r e s u l t s f or A1 7075-T6 wh i c h h a d b e e n p a s s i v a t e d i n 1000 p p m CeC13 f or o n e we e k a n d t h e n e x- p o s e d t o a e r a t e d 0. 5N NaC1 f or 2h. Th e EI S d a t a ( c u r v e 1) a r e t h o s e f or a v e r y p a s s i v e s ur f a c e . Ex c e l l e n t a g r e e me n t i s o b s e r v e d wi t h t h e f i t d a t a ( c u r v e 2), wh i c h r e s u l t i n a v e r y h i g h v a l u e of Rp = 3.26 106 ~ - c m 2. F i g u r e 5 i l l u s t r a t e s t h e c h a n g e s of t h e i mp e d a n c e s p e c t r a wh i c h o c c u r wi t h i n- c r e a s i n g e x p o s u r e t i me . F o r t h e u n t r e a t e d A1 7075-T6 p i t s i n i t i a t e i n a s h o r t t i me wh i c h i s r e f l e c t e d i n t h e pr o- n o u n c e d i n c r e a s e of Ct i n t h e c a p a c i t i v e r e g i o n a n d t h e a p- p e a r a n c e of t h e t r a n s mi s s i o n l i n e - t y p e f r e q u e n c y d e p e n d - e n c e i n t h e l o w- f r e q u e n c y r e g i o n i n a g r e e me n t wi t h t h e p i t t i n g mo d e l (Fi g. 1 a n d 2). Th e d a t a i n c u r v e 1 of Fi g. 5 s h o w s o me e r r a t i c c h a n g e s of t h e i mp e d a n c e mo d u l u s / Z / a n d t h e p h a s e a n g l e a t t h e l o we s t f r e q u e n c i e s . An a t t e mp t t o u s e t h e K- K t r a n s f o r ms t o v e r i f y wh e t h e r t h e s e d a t a a r e t r u e i mp e d a n c e d a t a f a i l e d i n t h e t r a n s mi s s i o n l i n e r e g i o n d u e t o t h e r e a s o n s di s - c u s s e d a b o v e . I t i s mo s t l i ke l y t h a t t h e dr i f t of t h e c or r o- s i o n p o t e n t i a l d u r i n g t h e me a s u r e me n t of t h e i mp e d a n c e c u r v e l e d t o p o l a r i z a t i o n of t h e e l e c t r o d e wh e n t h e l ow- f r e- 5 2 4 3 2 2 1 o - 6 - 5 - 4 - 3 - 2 - i 0 t 2 L o g f (f in HZ) 75 6 0 o 21 < 3 0 ~ m 0 3 4 5 F i g . 3 . B o d e p l o t s f o r A I 6 0 6 1 a f t e r e x p o s u r e t o 0 . 5 N N a C I f o r 2 4 h . C u r v e 1 , e x p e r i m e n t a l s p e c t r a ; c u r v e 2 , e x t r a p o l a t i o n o f t h e f i t t e d d a t a t o v e r y l o w f r e q u e n c i e s w i t h R , = 4 . 1 6 ~ , R p = 1 4 , 2 0 5 ~ , , C t o t ~ 1 7 5 I~F, R p~t/F = 2 4 2 6 , 0 , , K /F = 8 5 0 . 0 ~ ( t a d / s ) - n , a n d n = - 0 . 5 3 . 2 1 2 h ] Untreated 4 d AI 7 0 7 5 - T 6 coc, 3, . . . . . . 5 ~ 2 I AI 7075- T6 - 75 #n NaCI oJ 4 B o g N 3 45 ol <( -9 2 3 o ~ #_ i i N 0 I I I 0 - 2 - t 0 t 2 3 4 L o g f ( f i n H z ) Fig. 5. Bode plots for untreated and CeCI3-treated AI 7075- T6 dur- ing i m m e r s i o n i n 0 . 5 N N o C l . ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 155.69.4.4 Downloaded on 2014-08-11 to IP 80 J. El ect rochem. Soc., Vol . 137, No. 1, J anuar y 1990 9 The Electrochemical Society, Inc. i 4 2 1 1. CeCI 3 treated N 7 0 7 5 - T 6 2 . As ~ AI 7 0 7 6 - T 6 1 M ~ e I I I 1 0 2 0 3 0 4 0 Tzne ( days ) 5 " " , ! , , . . . U. U . = , 7 0 0 6 0 0 5 0 0 4 0 0 3 0 0 2 0 0 1 0 0 0 , m t t ~ for 2 , I 1 0 1. CeCI 3 t r e m d AI 7 0 7 5 - T 6 2 . Al l ~ N 7 0 7 5 - T 6 1 q P I I ~ / 2 0 3 0 4 0 T ~ e ( days ) Fig. 6 . Ti me dependence of R~ and R p i t / F (a, l ef t ) , and Ct (b, right) for AI 7 0 7 5 - T 6 (as-received v s . CeCI~ treatment) during exposure to NaCI quency data were measured. For these reasons these data points were not considered i n the analysis of the measured i mpedance spectra. For the passivated sample the i mpedance data are mai nl y capacitive (curve 3 in Fig. 5) unt i l pits initiate. An i ndi cat i on of pit initiation is given i n the spect rum for 23 days of exposure (curve 4). Figure 6 shows the results of the fit of the data for A1 7075-T6. Since it is not possible with the present fit procedure to det ermi ne the value of F and to calculate Cp and Cpit separately, the fit data are plot- ted as R p i t / F and Ct. For the CeC13-treated sample Rp has high values which increase when pits initiate. This is most likely due to cathodic protection of the passive surface by the pits (Fig. 6a). Rpit/F showed a cont i nuous decrease unt i l the test was stopped. The experi ment al values of the ca- pacitance Ct remai ned constant unt i l pits had initiated at which time Ct started to increase (Fig. 6b). This change oc- curred a few days before pits were detected visually, which is the time indicated in Fig. 6b. For the unt reat ed A1 7075 the increase of Ct was much larger and was obviously domi nat ed by the increase of FCpit. In order to obtain further information concerni ng the pit growth kinetics from the results shown i n Fig. 6, the value of F was det ermi ned visually at the end of the test. In addi- tion, the value of FCpit was det ermi ned from the data in Fig. 6b at the end of the test assumi ng that Cp, which did not change i n the time before pits initiated, also remai ns const ant duri ng the entire test. Based on a const ant value of Cpit (in ~F/cm 2) it is t hen possible to calculate F as a func- t i on of exposure time. In the same m a n n e r R p i t (in t2 9 cm 2) can be calculated. The results of this procedure are shown i n Fig. 7a for 1 / R p i t and K and in Fig. 7b for F and n. In addi- tion to the results for A1 7075-T6 data are also shown for A1 6061 which was deoxidized before passivation (see below). For both alloys pit growth rates decrease with time (Fig. 7a). A value of R p i t = 100 ~" c m 2 corresponds to a pit growth rate of about 2.2 mm/yr. The parameter K of the t ransmi ssi on line term can be assumed to be i ndependent 10 -1 Y 13 AI 6061(deoxidized)/CeCI 3 , A AI 7 0 7 5 - T 6 / Ce CI 3 , o ~ 10 I I I I 20 40 60 T I M E ( d a y s ) O ' r i - - O I 10 A I 6 0 6 1 ( d e o x i d i z e d ) / C e C I 3 ( l m ) , a A I 7 0 7 5 - T 6 / C e C I 3 , o I I [ [ I 3 0 5 0 7 0 T I M E ( d a y s ) Fig. 7. Ti me dependence of 1 / R r ~ t and K (a, l ef t ) and n and F (b, right) for AI 7 0 7 5 - T 6 and AI 6061 tO ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 155.69.4.4 Downloaded on 2014-08-11 to IP d. E l e c t r o c h e m . So c . , Vol . 137, No. 1, J anuar y 1990 9 The Electrochemical Society, Inc. 81 o f t i me , b u t i s ma t e r i a l d e p e n d e n t (Fi g. 7b)Y F i n c r e a s e s f r o m a b o u t 1% t o a b o u t 4% i n b o t h cas es , wh i l e n h a s v a l u e s c l os e t o - 0. 5. Th e c o n s t a n t v a l u e s of Cpit we r e 133 ~ F / c m 2 f or A1 7075-T6 a n d 105 ~ F / c m 2 f or A1 6061. Th e p r e t r e a t me n t of t h e A1 s u r f a c e s b e f o r e e x p o s u r e t o CeC13 c o n s i s t e d u s u a l l y of a d e o x i d i z i n g p r o c e s s . Th e r e- s u l t s f or A1 6061 a r e s h o wn i n Fi g. 7. I n a n e v a l u a t i o n of t h e e f f e c t of t h e p r e t r e a t me n t p r o c e d u r e s a mp l e s of A1 6061 wh i c h h a d b e e n o n l y d e g r e a s e d b e f o r e e x p o s u r e t o CeC13 we r e al s o t e s t e d . Du r i n g i mme r s i o n i n CeC13 n o s i g n i f i c a n t d i f f e r e n c e s we r e o b s e r v e d f or t h e t wo t y p e s o f s ur f a c e s . Ho we v e r , a ma r k e d i mp r o v e me n t of t h e c o r r o s i o n r e s i s t - a n c e i n NaC1 o c c u r r e d (5) f or t h e s a mp l e wh i c h h a d b e e n d e g r e a s e d o n l y (Fi g. 8). Th e i mp e d a n c e a t t h e l o we s t f r e- q u e n c i e s wa s h i g h e r a f t e r e x p o s u r e f or o n e mo n t h i n NaC1 ( c u r v e 6) f or t h e s a mp l e wi t h o u t t h e d e o x i d i z i n g p r e t r e a t - me n t a n d o n e we e k i mme r s i o n i n CeC13 t h a n t h a t a f t e r 2h i n NaC1 f or t h e s a mp l e wi t h t h e d e o x i d i z i n g t r e a t me n t a n d o n e mo n t h i mme r s i o n i n CeC13 (5). Th e l o w f r e q u e n c y d a t a i n Fi g. 8 s u g g e s t t h a t p i t t i n g d i d n o t o c c u r f or t h e pa s s i - v a t e d s a mp l e . Th e s e r e s u l t s gi ve s o me i n f o r ma t i o n c on- c e r n i n g t h e p r o c e s s b y wh i c h t h e CeCI~ t r e a t me n t i m- p r o v e s t h e c o r r o s i o n r e s i s t a n c e of A1 s ur f a c e s . Ap p a r e n t l y , t h e n a t u r a l o x i d e f i l m mu s t b e p r e s e n t wh i c h i s t h e n c o n - v e r t e d i n t o a mo r e c o r r o s i o n r e s i s t a n t s u r f a c e wh i c h c o n - t a i n s c e r i u m o x i d e s a n d h y d r o x i d e s . F o r A1/ Si C a n i n c r e a s e o f t h e c o r r o s i o n r e s i s t a n c e i n NaC1 d u e t o t h e p a s s i v a t i o n i n CeC13 wa s a l s o o b s e r v e d (Fi g. 9). T h e r e s i s t a n c e of t h e p a s s i v a t e d s a mp l e t o p i t t i n g wa s mu c h i mp r o v e d i n c o mp a r i s o n t o t h e b a r e A1/ Si C wh i c h s h o ws i mp e d a n c e s p e c t r a wh i c h a r e t y p i c a l f or t h e c a s e o f l oc a l i z e d c o r r o s i o n . Th e c o r r o s i o n r e s i s t a n c e of t h e p a s s i v a t e d A1/ Si C t e n d s t o d e c r e a s e wi t h t i me . Th i s mi g h t b e d u e t o c r e v i c e c o r r o s i o n wh i c h wa s d e t e c t e d at t h e e n d o f t h e t e s t a f t e r t h r e e mo n t h s u n d e r t h e o- r i ng wh i c h pr o- v i d e d a s e a l b e t we e n t h e t e s t cel l a n d t h e s a mp l e . S i mi l a r r e s u l t s h a d b e e n o b t a i n e d e a r l i e r f or a n o d i z e d A1/ Si C (18). S i n c e c r e v i c e c o r r o s i o n d i d n o t o c c u r f or a n y o f t h e o t h e r A1 a l l oys a n d Al - b a s e d M:MCs, i t wa s c o n c l u d e d t h a t i t wa s t h e r e s u l t o f t h e p r e s e n c e of t h e Si C p a r t i c u l a t e s . F o r A1/ Gr, i mme r s i o n i n CeC13 a l s o p r o d u c e d a v e r y cor - r o s i o n r e s i s t a n t s u r f a c e wi t h a ma r k e d i mp r o v e me n t o v e r t h e u n t r e a t e d s u r f a c e (Fi g. 10). Af t e r 2 h i mme r s i o n i n NaC1, ma i n l y c a p a c i t i v e b e h a v i o r wa s o b s e r v e d f or t h e p a s s i v a t e d A1/ Gr wi t h Rp e x c e e d i n g 4 104 ~ ( 8 . 1 0 5 9 cm2). T h e s p e c t r a d i d n o t c h a n g e s i g n i f i c a n t l y d u r i n g i mme r s i o n f or a b o u t 50 da ys . Af t e r t h i s t i me t h e l ow- f r e- q u e n c y p a r t of t h e s p e c t r a c h a n g e d i n a ma n n e r wh i c h i n- d i c a t e d t h a t p i t t i n g h a d o c c u r r e d ( c u r v e 4 i n Fi g. 10). At t h e s a me t i me b l i s t e r i n g of t h e A1 f a c e s h e e t wa s o b s e r v e d a n d g a s e v o l u t i o n o c c u r r e d o c c a s i o n a l l y f r o m s o me i s o l a t e d s p o t s o n t h e s ur f a c e . I t i s i n t e r e s t i n g t o n o t e t h a t t h e me a s - u r e d e l e c t r o d e c a p a c i t a n c e d i d n o t c h a n g e v e r y mu c h dur - I n Ref. (15) i t was assumed t hat W was proport i onal to F r at her t han t o 1IF. Thi s leads t o an erroneous t i me dependence of K i n Ref. (19) (Fig. 7b). 9 0 1 4h A1606t , 2 l d | degreasecl only, 5 3d 9 unt reat ed. 5 4 l d AI6061, 5 7 d ) degreased only, 6 l m CeCI3 t reated. 4 In NaCI 5 N 3 2 4,5,6 4,5,6 ! 0- - 2 - t 0 t 2 3 4 L o g f ( f t n HZ } Fig. 8 . Bode plots for untreated and CeCI3-treated (degreased A I 6061 as a functi on of e xpos ur e t i me t o 0 . 5 N NaCI. 7 5 60 c~ 45 m so ~ 0- 0 6 90 2 l m ) AI / SiC' untreal 5 4 3 ml Ce Cl 3 t r e a t e d In Na CI g N 3 45 03 a 3o~ O_ 1 t 5 0 0 - 2 - i 0 1 2 3 4 5 L o g f ( f i n H z ) Fig. 9 . Bode plots for untreated and CeCI3-treated AI / S i C as a f unc- t i on of exposure t i me t o 0 . 5 N Na CI . 90 3 1 d 2 6d ) AI / Gr'untreak 3 2 h l A i / G r 75 5 4 5 5 d CeCI3t'reated o g N 3 45 m < o 2 - 30 ~ m t t 5 0 0_ 2 I I I I - 1 0 1 2 3 d L o g f ( f i n HZ) Fig. 10. Bode plots for untreated and CeCI3-treated A I / G r as a f unc- t i on of exposure t i me t o 0 . 5 N NoCI . i n g t h i s t i me wh i c h i n d i c a t e s t h a t t h e c o r r o s i o n p r o c e s s a t t h e AYg r a p h i t e g a l v a n i c c o u p l e d i d n o t p r o d u c e a l a r ge v a l u e of Cpit. F o r t h e u n t r e a t e d A1/ Gr p i t t i n g c o r r o s i o n wa s a l r e a d y i n- d i c a t e d a f t e r o n e d a y o f e x p o s u r e t o NaC1 (Fi g. 10). Th e l o w- f r e q u e n c y d a t a k e p t c h a n g i n g d u r i n g t h e s i x d a y e x- p o s u r e t i me a n d s h o we d a f r e q u e n c y d e p e n d e n c e of t h e mo d u l u s / Z / a n d t h e p h a s e a n g l e wh i c h i s p r e d i c t e d b y t h e mo d e l i n Fi g. 1. I t wi l l b e n o t e d , h o we v e r , t h a t c o n t r a r y t o t h e u s u a l l a r ge i n c r e a s e of t h e e x p e r i me n t a l v a l u e s of t h e c a p a c i t a n c e p r a c t i c a l l y n o c h a n g e o c c u r r e d f or s i x d a y s of t h e u n t r e a t e d s a mp l e . Th e o f t e n d r a ma t i c e f f e c t s of i mme r s i o n i n 1000 p p m CeC13 o n t h e c o r r o s i o n r e s i s t a n c e a r e s h o wn i n Ta b l e I wh i c h c o mp a r e s t h e t i me s a t wh i c h p i t t i n g wa s f i r s t de - t e c t e d f or u n t r e a t e d a n d t r e a t e d s a mp l e s . Wi t h o u t t h e pa s - s i v a t i o n t r e a t me n t p i t s i n i t i a t e d i n l e s s t h a n o n e d a y f or al l ma t e r i a l s , wh i l e p a s s i v a t e d s a mp l e s c o u l d s u r v i v e e x p o - T a b l e I . Comparison of pitting times (tp = pitting time; tc = crevice t i me in days) Material Pr et r eat ment CeC13 t r eat ed Unt r eat ed A1 7075-T6 Deoxi di zed tp > 24 tp < 1 A16061 Deoxidized tp < 3 t , < 1 A1 6061 a Deoxi di zed tp > 29 A1 6061 Degreased t p > 90 tp < 1 A1 6061/SIC Deoxi di zed tp > 81 tp < 1 t c > 8 A1 6061/Graphite Deoxi di zed tp > 40 tp < 1 only) a On e mo n t h CeCl a t r e a t me nt . ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 155.69.4.4 Downloaded on 2014-08-11 to IP 82 J. El ect r ochem. Soc., Vol. 137, No. 1, Januar y 1990 9 The Electrochemical Society, Inc. sure to NaC1 for one to three mont hs wi t hout pitting. For SiC/A1 crevice corrosion was observed after eight days, but pits did not occur in 81 days. Summary and Conclusions Localized corrosion in the form of pitting and/or crevice corrosion occurring for A1 alloys and Al-based metal ma- trix composi t es can be detected by characteristic features of t he EIS data. A pitting model has been devel oped whi ch is in agreement with the experi ment al data. A fitting pro- cedure is available for the analysis of such data. Furt her ef- forts will be devot ed to the separate det ermi nat i on of the polarization resistance of the growing pit R p i t and the area fraction F on whi ch pitting occurs. At present, this has only been possible if F was det ermi ned virtually at the end of the test and if it was assumed that Cp and Cpit did not change with exposure time. Immersi on of A1 7075-T6, A1 6061, A1 6061/SIC, and A1 6061/graphite in 1000 ppm CeC13 for one week markedl y i mproves the resistance of these materials to localized cor- rosion. For passivated A17075-T6 pitting did not occur dur- ing i mmersi on in aerated 0.5N NaC1 for three weeks, while t he as-received alloy pitted in a few hours. The corrosion resistance of the passivated sample was similar to that of a surface whi ch had been treated with a commerci al chro- mat e conversi on coating (5). This result suggests that pas- sivation in CeC13 is an alternative to the use of chromat e conversi on coatings for A1 alloys. Work is in progress at evaluating other rare earth chlorides as medi a for passi- vation. Acknowledgments Thi spr oj ect is support ed by the Army Research Office under Contract No. DAAL 03-86-K-0156 and by t he Office of Naval Research under Contract No. N00014-88-K-0034. Manuscript submi t t ed Feb. 14, 1989; revised manuscri pt received May 30, 1989. This was Paper 187, present ed at the Chicago, IL, Meeting of the Society, Oct. 9-14, 1988. The Uni versi t y of Sout hern Cal i f orni a asssited i n meet- i ng the publ i cat i on costs of this article. REFERENCES 1. F. Mansfeld and M. Kendig, ASTM STP, 866, 122 (1985). 2. F. Mansfeld and M. W. Kendig, This Journal , 135, 828 (1988). 3. F. Mansfeld, M. Kendig, and W. J. Lorenz, ibid., 132, 29O (1985). 4. K. J~ttner, W. J. Lorenz, M. W. Kendig, and F. Mans- feld, ibid., 135, 332 (1988). 5. F. Mansfeld, S. Lin, S. Kim, and H. Shih, Paper 380 present ed at "Corrosion/88." 6. F. Mansfeld, S. Lin, S. Kim, and H. Shih, Corr. Sci., 27, 997 (1987). 7. F. Mansfeld and H. Shih, This Journal , 135, 1171 (1988). 8. H. Shih and F. Mansfeld, Corrosion, 45, 610 (1989). 9. B. R. W. Hinton, D. R. Ryan, and N. E. Ryan, Metals Forum, 7, 211 (1984). D. R. Arnott, N. E. Ryan, B. R. W. Hinton, B. A. Sexton, and A. E. Hughes, Appl . Surf. Sci., 22, 236 (1985). B. R. W. Hinton, N. E. Ryan, D. R. Arnott, P. N. Tra- then, L. Wilson, and B. E. Williams, Corros. Aust ra- lasia, 10, 12 (1985). D. R. Arnott, B. R. W. Hinton, and N. E. Ryan, Corro- sion, 45, 12 (1989). H. Shih and F. Mansfeld, Corros. Sci., In press. M. Kendi g and F. Mansfeld, Corrosion, 39, 466 (1983). F. Mansfeld, S. Lin, Y. C. Chen, and H. Shih, This Jour- nal, 135, 906 (1988). H. Shih and F. Mansfeld, Corr. Sci., 28, 933 (1988). H. Shih and F. Mansfeld, Corrosion, In press. F. Mansfeld and S. L. Jeanj aquet , Corr. Sci., 26, 727 (1986). F. Mansfeld, S. Lin, S. Kim, and H. Shih, in "Transi ent Techni ques in Corrosion Sci ence and Engineering, " (PV 89-1) W. H. Smyrl, D. D. Macdonald, and W. J. Lorenz, Editors, p. 390, The El ect rochemi cal Society Soft bound Proceedi ngs Series, Penni ngt on, NJ (1989). 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. Study of Passive Films Formed on AISI 304 Stainless Steel by Impedance Measurements and Photoelectrochemistry A. M. P. SimSes and M. G. S. Ferreira Depart ament o de Engenhari a Qui mi ca, Inst i t ut o Superi or T~cnico, 1096 Li sboa Codex, Port ugal B. Rondot and M. da Cunha Belo Centre d' Et udes de Chi mi e M~tallurgique du CNRS, 94407 Vi t ry-Sur-Sei ne, France ABSTRACT Mot t -Schot t ky plots and phot oel ect rochemi cal measurement s were made on films formed at different potentials on AISI 304 stainless steel in a borate/boric acid solution, pH 9.2. The results allowed t he det ermi nat i on of the semicon- duct i ve properties and band structure of the films, whi ch account for the exi st ence of two kinds of films dependi ng on the format i on potential. For potentials below 0 V (SCE), the results point out for a film with an inverse spinel structure consti- tuted by Cr-substituted magnet i t e with two donor levels. Above 0 V only one donor level is detected, whi ch should be Fe 2 on tetrahedral sites. The phenomenon of passivation of iron has been ex- plained by the formation of an oxide film having a struc- tural and a chemical nature that place it bet ween mag- netite (Fe~O4) and hemat i t e (Fe203) (1-4). This analysis is in good agreement with the t hermodynami c data from elec- t rochemi cal equilibria diagrams (5) and is support ed by experi ment al electron diffraction studies (6-7). The prob- l em of characterization of this passive film in t erms of stoi- chi omet ry and of distribution of cationic and anionic spe- cies in the crystallographic lattice of the oxide is still a controversial subject, although the idea of a spinel type of st ruct ure subsists. On the contrary, the structural characterization of pas- sive films on stainless steels remains far from clarified. Not only is in this case the t hermodynami cal approach com- plex, but also the exami nat i on of the structural organiza- tion reveals itself as more difficult. The absence of diffrac- tion diagrams typical of a crystalline structure does not necessarily mean that the film is amorphous (8), although the protective behavior of amorphous materials is con- sidered better than that of crystalline ones. On the other hand, the t erm "amorphous" covers a mul t i t ude of struc- tural states correspondi ng to several short distance de- grees of order, whose identification demands the use of ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 155.69.4.4 Downloaded on 2014-08-11 to IP