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ABSTRACT
A finite difference n u m e r i c a l analysis technique has b e e n used to e v a l u a t e
the d i s t r i b u t i o n of the electrode p o t e n t i a l w i t h i n the e l e c t r o l y t e above a g a l -
vanic corrosion couple w i t h linear, semi-infinite, c o p l a n a r electrodes. C o r r o -
sion reactions a r e a s s u m e d to be u n d e r activation control w i t h l o g a r i t h m i c
p o l a r i z a t i o n behavior. The analysis accommodates a n y c o m b i n a t i o n of elec-
trochemical p o l a r i z a t i o n p a r a m e t e r s , corrosion c u r r e n t densities, solution
conductivity, electrode dimensions, a n d d e p t h of corrosion solution as v a r i a b l e
parameters. F u r t h e r , the analysis has been a d a p t e d to include the influence
of an e x t e r n a l l y i m p r e s s e d polarization. The accuracy of t h e analysis p r o -
c e d u r e has b e e n established b y c o m p a r i s o n w i t h e x p e r i m e n t a l r e s u l t s o b t a i n e d
f r o m a m o d e l z i n c - c o p p e r galvanic corrosion couple. The effects of various
p a r a m e t e r s on the electrode potential d i s t r i b u t i o n at the surface of the c o r r o -
sion couple h a v e been e x a m i n e d and their significance discussed.
2057
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2058 J. Electrochem. Soc.: E L E C T R O C H E M I C A L SCIENCE AND TECHNOLOGY December I979
t EA _ t z=O
w
O I
"E
W electrolyte
O
Z Q.
O
"O
2
I x uu EB
- I
I
4 .Q b 9
,q
-a o
b
Fi$. I. Schematic diagram showing the arrangement of electrodes Distance x
in the corrosion couple. Element A is the cathode and element B is Fig. 3. Schematic diagram showing the electrode potential dis-
the anode. tribution in solution across the surface of the galvanic corrosion
couple shown in Fig. 1.
The various c u r r e n t vs. electrode p o t e n t i a l r e l a t i o n -
ships for the anodic a n d cathodic reactions a r e assumed z -- 0 is i l l u s t r a t e d s c h e m a t i c a l l y in Fig. 3. A t distances
to be s u b j e c t to activation control w i t h l o g a r i t h m i c x < 0, anodic c u r r e n t is c o m p l e m e n t e d and effectively
(Tafel) p o l a r i z a t i o n behavior. P o l a r i z a t i o n c h a r a c t e r - r e d u c e d b y an excess cathodic c u r r e n t g e n e r a t e d on
istics of the anodic a n d the cathodic reactions for each e l e m e n t A.
e l e m e n t of the corrosion couple are shown schemati- Since t h e r e is no a c c u m u l a t i o n or loss of ions in the
cally in Fig. 2. Thus the n e t cathodic c u r r e n t density p e r b u l k of the e l e c t r o l y t e the d i s t r i b u t i o n of electrode
unit l e n g t h of corrosion couple, /~(x), on e l e m e n t A at p o t e n t i a l w i t h i n the e l e c t r o l y t e m u s t satisfy Laplace's
a n electrode p o t e n t i a l Ex is equation
i~(x) = ~o(A) {exp ((EA -- E x ) / ~ A ) V~E = 0 C3]
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Vol. 126, No. 12 NUMERICAL ANALYSIS OF CORROSION 2059
z,,O
w = 0.01
0.2
E;V
0446 .0.146
i
-0-01 0 X; m 0.01
0.188 '@glg
- 0.01 0 0.01
X;m
z=w= 0-01
0-1
Fig. 4. Computer analysis results showing: (a, upper left) equipo-
tential distribution, (b, upper right) electrode potential in solution
vs. x at z - - 0, and (e, lower left) electrode potential vs. x at z - -
E;V w - - 0.01rn for an electrode couple with C~A = '~B = f A = fiB - -
0.0$V, C ~ 10 ~ - 1 m - 1 , io(A) - - io(B) = 1 Am - 2 , a = b - -
w = 0.01m, and EA = - - E B - - 0.SV.
I
-0.0~ \ 0-01
X;m
W 4.500
I
J 4"083
I .1.0 z=O
I 3.667
E3=4.5V
3.25!
E;V
J
2.835
0.5
2.419
2.003
1.587 X;m
1.171
- - 0.754 corrosion
0.388 .1_-0.5
-@01 0 (~01
X;m
Fig. 5. Computer analysis results showing: (a, left) the equipotential distribution above the galvanic corrosion couple described in Fig. 4
with an applied anodic polarization E8 = -t-4.5V, and (b, right) electrode potential in solution vs. x at z = 0 for both open-circuit free
corrosion and applied anodic polarization.
surface is shifted in the direction of the a p p l i e d p o l a r i - filled w i t h solution to depths of 2 and 20 mrm T h e dis-
zation b u t its g e n e r a l form is p r e s e r v e d w i t h the c a t h - tribution of electrode p o t e n t i a l across the couple w a s
odic e l e m e n t r e m a i n i n g cathodic to the anodic element, m e a s u r e d using a reference m i c r o e l e c t r o d e (Ag/AgC1)
however, in this ca~e, the g r a d i e n t d E / d x is increased (1, 2, 17) w i t h probe d i a m e t e r ~ 0.1 mm, a c c u r a t e l y
in the region of the couple interface x -----0, w h e n c o m - positioned using a m i c r o m a n i p u l a t o r . Distributions
p a r e d w i t h the free corrosion condition, Fig. 5 (b). w e r e m e a s u r e d at solution depths corresponding to
z : 1 m m a n d w. The electrode p o t e n t i a l of the r e f e r -
Experimental Test of the Numerical Solution ence m i c r o e l e c t r o d e was m e a s u r e d to be + 100 +__2 mV
The analysis described above has been a p p l i e d to w i t h r e f e r e n c e to a s a t u r a t e d calomel electrode. A l l
a copper-zinc g a l v a n i c couple corroding in a 0.01M m e a s u r e d potential values a r e r e p o r t e d w i t h r e f e r e n c e
h y d r o c h l o r i c acid solution. The e x p e r i m e n t a l cell, to the s a t u r a t e d calomel electrode scale.
shown s c h e m a t i c a l l y in Fig. 6, comprises an open P e r - The polarization p a r a m e t e r s for zinc and copper in
spex vessel placed across the copper-zinc couple and 0.01M hydrochloric acid h a v e been m e a s u r e d (1) and
these a r e listed in Table I t o g e t h e r w i t h the solution
conductivity C. These values w e r e used in the n u m e r i -
cal analysis to calculate the e q u i p o t e n t i a l distribution
a b o v e the e x p e r i m e n t a l corrosion couple a n d t h e r e -
Electrometer sults o b t a i n e d for the two solution depths a r e shown
in Fig. 7. F i g u r e 8 shows t h e e x p e r i m e n t a l results o b -
t a i n e d for the electrode potential vs. x at z = 1 m m
and w for both solution depths s u p e r i m p o s e d on the
Microelectrode analysis results.
Both the calculated and m e a s u r e d e q u i p o t e n t i a l dis-
tributions a r e different for the two solution depths. The
e q u i p o t e n t i a l d i s t r i b u t i o n a b o v e t h e 2 m m d e p t h [Fig.
7 ( a ) ] is almost i n d e p e n d e n t of z, i.e., t h e c u r r e n t flow
Zn Cu
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Vol. 126, No. 12 NUMERICAL ANALYSIS OF CORROSION 2061
,0 oo0 e-
l , , 0 -0.948
W
0.962
-0.934
- 0.969
-0.920
-0.906
a
| a 0 b
0 b
X~
X --~
Fig. 7. Calculated equipotential distribution above the experimental copper-zinc corrosion couple for solution depths: (a, left) w ~ O.O02m
and (b, right) w - - O.02m.
zm lmm
Cu E;V s.c.e. Zn
Cu E ;Vs.c.e. Zn
w, 2mm
w,2mm
.-0-90
.0.90
w:2Omm
I I ,
-5 0 5 X:mm 10 15 20 -5 0 5 X ; m m 10 15 20
Fig. $. Calculated curves and experimental points showing the electrode potential Ys. x at: (a, left) z _-- 1 mm and (b, right) z ~ w for w
- - 2 and 20 ram.
i n solution is p r i m a r i l y i n the -+- X direction, whereas The distribution of electrode potential for z > 0
the d i s t r i b u t i o n above the 20 m m depth example [Fig. w i t h i n the corrosion cell is i m p o r t a n t only insofar as it
7 ( b ) ] is highly d e p e n d e n t on z. The very good agree- is this which can be measured directly with a n ex-
m e n t observed b e t w e e n the m e a s u r e d and the cal- t e r n a l reference electrode via a Luggin probe. This
culated electrode potential vs. x plots in Fig. 8 support volume distribution is a result of the electrode poten-
the accuracy a n d validity of this n u m e r i c a l analysis tial variation across the surface of the galvanic corro-
procedure. sion couple at z : 0. It is this latter distribution which
Discussion describes the kinetics and localization of the corrosion
The e x p e r i m e n t a l results show the present finite dif- reactions. Clearly, both the volume and associated sur-
ference method of n u m e r i c a l analysis to be capable of face distributions of electrode potential are dependent
e v a l u a t i n g the distribution of electrode potential above on all of the above electrochemical parameters and
a coplanar galvanic corrosion couple i n which the elec- physical dimensions (Fig. 4-8).
trode reactions are subject to activation control. A p - The distribution of electrode potential across a gal-
plication of such a n analysis requires an e x p e r i m e n t a l vanic corrosion couple describes the localization of the
d e t e r m i n a t i o n of the various electrochemical p a r a m - corrosion reaction; consequently, a n y consideration of
eters describing the electrode reactions of each com- corrosion behavior requires a knowledge of this dis-
p o n e n t of the couple, the value of a n y applied polariza- tribution. The present analysis procedure allows this
tion, as well as the physical dimensions of the corro- to be calculated using e x p e r i m e n t a l l y d e t e r m i n e d
sion cell. polarization behavior from a n y combination of elec-
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2062 J. E $ e c t r o c h e m . Soc.: E L E C T R O C H E M I C A L S C I E N C E A N D T E C H N O L O G Y D e c e m b e r I979
ol
6 ~ 6 o
W
ILII
IIII W
Illl
1/I
!
-0-01 0 0-01
0.020 -0020
X;m
0-100 -0-100
0-4 z:0
%
0.180 -0.180
-0.01 0 0.01
E;V
X;m
0.2
-0-2
w: 0.001
-0.4
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Vol. 126, No. 12 NUMERICAL ANALYSIS OF CORROSION 2063
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