Pitting and Passivation of AI Alloys and AI-Based

Metal Matrix Composites

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.
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' 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 .
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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
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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 .
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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
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997 (1987).
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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
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