A Finite Difference Numerical Analysis of

Galvanic Corrosion for Semi-Infinite

Linear Coplanar Electrodes
P. Doig and P. E. J. Flewitt
CentraZ Electricity Generating Board, South Eastern Region,
Scientific Services Department, Gravesend, Kent, England

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.

The d i s t r i b u t i o n of e l e c t r o d e p o t e n t i a l across the the finite difference technique, however, r e c o m m e n d s

surface of heterogeneous corroding electrodes is of
f u n d a m e n t a l i m p o r t a n c e in describing the localization
and kinetics of n o n u n i f o r m corrosion phenomena. In
general, corrosion of service components can occur
u n d e r various o p e r a t i n g conditions r a n g i n g from v e r y
shallow condensed layers to b u l k v o l u m e solutions.
Previous p a p e r s (1, 2) h a v e e v a l u a t e d a n a l y t i c a l l y the
distributions of electrode p o t e n t i a l across coplanar
corrosion couples in w h i c h the electrode reactions a r e
s u b j e c t to a c t i v a t i o n control. I n o r d e r to achieve an
a n a l y t i c a l solution, ion c u r r e n t flows w i t h i n t h e so-
lution w e r e r e s t r i c t e d to the p l a n e of t h e electrode
surface. A l t h o u g h v a l i d for s h a l l o w corrosion solutions
w i t h m o d e r a t e conductivity, such a r e s t r i c t i o n is;' not
a d e q u a t e for the m o r e g e n e r a l case of corrosion u n d e r
b u l k solutions w h e r e c u r r e n t flows n o r m a l to the cor-
r o d i n g electrode surface become significant.
A n u m b e r of o t h e r analyses h a v e been d e v e l o p e d
which e i t h e r a r e based on l i n e a r p o l a r i z a t i o n kinetics
(3-9) w i t h o r w i t h o u t the a d d i t i o n a l r e q u i r e m e n t of
s i m i l a r p o l a r i z a t i o n p a r a m e t e r s for the anodic a n d
cathodic e l e c t r o d e reactions, or assume g e n e r a l Tafel
kinetics (10) w i t h equal anodic and cathodic p o -
l a r i z a t i o n p a r a m e t e r s . As discussed p r e v i o u s l y (1, 2),
the assumption of l i n e a r p o l a r i z a t i o n kinetics is not
v a l i d for m a n y corrosion reactions w h e r e the
electrode reactions are s u b j e c t to activation con-
trol r e s u l t i n g in l o g a r i t h m i c p o l a r i z a t i o n b e h a v i o r
w h i c h is r a r e l y s i m i l a r for both t h e anodic and c a t h -
odic reactions. A t p r e s e n t t h e r e is no a n a l y t i c a l p r o -
cedure a v a i l a b l e w h i c h can g e n e r a l l y a c c o m m o d a t e
different l o g a r i t h m i c polarizations such t h a t it becomes
necessary to a d o p t a n u m e r i c a l technique. T h e r e are
two basic techniques a v a i l a b l e for such analysis. The
e a r l i e r a n d p e r h a p s s i m p l e r of these is b a s e d on the
finite difference technique of Solution b y successive
i t e r a t i o n or r e l a x a t i o n (11). This t e c h n i q u e has been
shown t h e o r e t i c a l l y to be s u i t a b l e for the e v a l u a t i o n
of the e l e c t r o d e p o t e n t i a l in t w o - d i m e n s i o n a l electro-
chemical cells (12). More recently, the finite e l e m e n t
technique has been d e v e l o p e d (13) a n d shown to be
p a r t i c u l a r l y efficient w h e n a p p l i e d to electrochemical
processes w h i c h r e s u l t in significant changes in the
electrode g e o m e t r y (14). The r e l a t i v e s i m p l i c i t y of
Key words: corrosion, copper, numerical analysis, cathodic pro-
~ection, potentiostatic control, zinc.
its a p p l i c a t i o n to g e n e r a l corrosion p h e n o m e n a w h e r e
such shape changes a r e not of p r i m e significance a n d
are small in r e l a t i o n to the o v e r - a l l corrosion cell di-
mensions.
This p a p e r describes the a p p l i c a t i o n of a n u m e r i c a l
finite difference m e t h o d to the e v a l u a t i o n of electrode
potential d i s t r i b u t i o n w i t h i n the e l e c t r o l y t e a b o v e a
coplanar, linear, semi-infinite corrosion couple in
which the electrode reactions a r e s u b j e c t to activation
control w i t h different p o l a r i z a t i o n p a r a m e t e r s . This
corrosion couple g e o m e t r y was chosen to s i m u l a t e the
p h e n o m e n o n of i n t e r g r a n u l a r corrosion w h i c h results
from either s e c o n d - p h a s e p r e c i p i t a t i o n or selective
solute segregation to the g r a i n b o u n d a r i e s b r o u g h t
about b y s t r e n g t h e n i n g h e a t - t r e a t m e n t s , fabrication,
or component service. Here, the g r a i n b o u n d a r y region
m a y be either anodic or cathodic to the m a t r i x and the
d i s t r i b u t i o n of the electrode reactions is of i m p o r t a n c e
in creating surface defects which m a y develop into
incubation sites for s u r f a c e - i n i t i a t e d f a i l u r e processes
such as fatigue a n d stress corrosion cracking.
The p r e s e n t analysis considers not only the free cor-
rosion condition b u t includes a facility for s i m u l a t i n g
the effects of an e x t e r n a l l y a p p l i e d s u p e r i m p o s e d p o -
larization. Results o b t a i n e d from the free corrosion
n u m e r i c a l analysis a r e c o m p a r e d w i t h e x p e r i m e n t a l
results o b t a i n e d from a model copper-zinc galvanic
corrosion couple. The influence of the various e x p e r i -
m e n t a l p a r a m e t e r s , in p a r t i c u l a r the solution d e p t h and
a p p l i e d polarization, on the d i s t r i b u t i o n of electrode
p o t e n t i a l a r e discussed.
Analysis of the Electrode Potential Distribution
The p r e s e n t analysis is b a s e d on a m o d e l galvanic
corrosion couple consisting of two semi-infinite, co-
planar, strip elements shown s c h e m a t i c a l l y in Fig. 1.
The electrode surface lies in the XY p l a n e and is infinite
in the ___ Y directions. The couple consists of a cathodic
e l e m e n t A of w i d t h a in the -- X direction and anode B
of w i d t h b in the -{- X direction covered b y an elec-
t r o l y t e of d e p t h w in the -~ Z direction. The electrolyte
is b o u n d e d by perfect insulators at z = w a n d x --
-- a and -{- b. The s y m m e t r y of the electrode configura-
tion constrains all c u r r e n t flow to the XZ p l a n e such
that the analysis is r e d u c e d to a t w o - d i m e n s i o n a l p r o b -
lem.

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]

-- e x p ( ( E A - - Ex)/--aA)) [1] s u b j e c t to the following b o u n d a r y conditions:

w h e r e EA is t h e f r e e c o r r o s i o n p o t e n t i a l of e l e m e n t .%,
io(A) is the free corrosion c u r r e n t density, a n d aA a n d
/~A a r e the Tafel p a r a m e t e r s for the anodic and c a t h -
odic reactions, respectively. S i m i l a r l y for e l e m e n t B,
the net anodic c u r r e n t d e n s i t y p e r unit l e n g t h of cor-
rosion couple, ta(x), o n e l e m e n t B at an electrode p o -
t e n t i a l Ex is
i,.(z) = io(B) {exp( (Es - - E z ) / - - a B )
-- exp((Es -- Ex)/~B)}
w h e r e EB is the free corrosion p o t e n t i a l of e l e m e n t
B, io(B) iS the free corrosion c u r r e n t density, a n d aB
and fib a r e the anodic and the cathodic Tafel p a r a m -
eters. Thus, anodic c u r r e n t flows w i t h i n the e l e c t r o l y t e
from ti~e e l e m e n t B to e l e m e n t A following an electric
potential g r a d i e n t equal a n d opposite to the electrode
potential g r a d i e n t (dEx/dx). The e l e c t r o d e potential
d i s t r i b u t i o n across the corrosion couple surface at
EA _ _
> n u m e r i c a l solution of Laplace's equation. The p r e s e n t
~ c o m p u t e r p r o g r a m (16) allows the e x p e r i m e n t a l p a -
.=
O
aB
EB
m
Ill
I e x p a n d e d for c l a r i t y of presentation. F i g u r e s 4(b) a n d
Io(A) Io (B)
log e (current density) ; Am -2
Fig. 2. Schematic polarization curves for the two elements of the
corrosion couple shown in Fig. I. a and fl are the Tafel parameters
for the respective anodic and cathodic reactions.
F o r z -- 0 the n o r m a l d e r i v a t i v e of electrode p o t e n -
tial E is given b y
dE
dz for --a<x<O t
[4]
dE --ia(x)/C for 0<x<b
dz
w h e r e C is the conductivity of the corrosion electrolyte.
Since t h e r e is no c u r r e n t flow n o r m a l to the i n -
[2]
sulating b o u n d a r i e s
dE
..... = 0 at x=--a and + b [5]
dx
dE
"dz = 0 at z=w [6]
Equation [3] has been solved b y t h e finite difference
m e t h o d of successive o v e r - r e l a x a t i o n (15) using an
i t e r a t i v e n u m e r i c a l p r o c e d u r e on an IBM 370 c o m p u t e r
(11, 12, 16). This r e q u i r e d a notional r e c t a n g u l a r C a r -
tesian grid to be e s t a b l i s h e d o v e r t h e r e g i o n defined
b y the electrolyte. The potential values at the nodal
points, defined b y the intersection of t h e grid lines,
were t h e n d e t e r m i n e d b y i t e r a t i v e solution of the sys-
t e m of finite difference equations associated w i t h the
r a m e t e r s a, b, w, ~o(A), ioCB), EA, EB, ~A, aB, ~A, ~B, and
C to be specified by the user.
The p r o g r a m provides a g r a p h i c a l plot of equipo-
t e n t i a l lines across the-XZ p l a n e and the corresponding
electrode p o t e n t i a l vs. x values across selected g r i d
lines p a r a l l e l to the electrode surface including z = 0.
T y p i c a l results for a h y p o t h e t i c a l s y m m e t r i c a l c o r r o -
sion couple w i t h the given electrochemical p a r a m e t e r s
are shown in Fig. 4. F i g u r e 4 ( a ) shows t h e 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 in the XZ plane w i t h the dimensional scales
(c) show the electrode p o t e n t i a l vs. x plots for z = 0
(the electrode surface) and w (the solution surface),
respectively. The s y m m e t r y of t h e solutions o b t a i n e d
for a r a n g e of s i m i l a r p a r a m e t e r s p r o v i d e s confidence
in the a p p l i c a t i o n of the technique and confirms t h a t
the specified e r r o r of calculation was sufficiently s m a l l
to give accurate results.

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 Vol. 126, No. 12 NUMERICAL ANALYSIS OF CORROSION 2059

0.104 0.064 0 -0.064 -0.I04

W

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

I n practice t h e r e a r e m a n y corrosion situations of potential along the b o u n d a r y z = w to be a constant

technological i n t e r e s t in w h i c h the g a l v a n i c corrosion
couple is s u b j e c t to an e x t e r n a l a p p l i e d polarization,
e i t h e r g a l v a n i c o r potentiostatic, w h e r e the m i x e d elec-
t r o d e p o t e n t i a l of the corrosion couple is displaced from
its e q u i l i b r i u m value. Common e x a m p l e s include
cathodic protection and potentiostatic or galvanostatic
polarization m e a s u r e m e n t s . U n d e r these circumstances
the e l e c t r o d e p o t e n t i a l d i s t r i b u t i o n o v e r t h e corrosion
couple will be changed in a nonuniform, complex m a n -
ner. This change will influence the d i s t r i b u t i o n a n d i n -
tensity of the corrosion reactions on the electrode s u r -
faces. Such a p p l i e d polarization effects m a y be e x -
a m i n e d using the above analysis s i m p l y b y m o d i f y i n g
the b o u n d a r y condition, Eq. [6]. F o r t y p i c a l i n e r t
counterelectrodes, e.g., platinum, w i t h v e r y l o w p o l a r i -
zation p a r a m e t e r s a n d for values of w which a r e com-
p a r a b l e o r l a r g e w i t h respect to t h e e l e c t r o d e d i m e n -
sions, we can r e a s o n a b l y a p p r o x i m a t e the electrode
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E~. This v a l u e Es is a user definable v a r i a b l e in t h e
p r e s e n t c o m p u t e r p r o g r a m . This b o u n d a r y p l a n e s i m u -
lates the position of the c o u n t e r e l e c t r o d e w h i c h passes
that e x t e r n a l c u r r e n t r e q u i r e d to p r o d u c e the p o l a r i z a -
tion. The net e x t e r n a l c u r r e n t flow m a y be deduced
f r o m an i n t e g r a t i o n of the r e s u l t i n g electrode p o t e n -
tial vs. x plot for z : 0 and the c u r r e n t d e n s i t y Eq. [1]
and [2].
A n example of this analysis with a value of Es :
4.5V, is shown in Fig. 5 for the same variables as il-
lustrated in Fig. 4. Figure 5 (a) shows the equipoten-
tial distribution in the X Z plane, again with the Z axis
expanded for clarity, and Fig. 5(b) shows the elec-
trode potential across the surface of the galvanic couple,
i.e., z ---- 0 w h e n polarized and under free corrosion
conditions. Clearly, the over-all distribution of elec-
trode potential within the solution is significantly modi-
fied by the applied polarization. The distribution at the
 2060 J. EIectrochem. Sot.: ELECTROCHEMICAL SCIENCE AND TECHNOLOGY D e c e m b e r 1979

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 -
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 -
odic e l e m e n t r e m a i n i n g cathodic to the anodic element,
however, in this ca~e, the g r a d i e n t d E / d x is increased
in the region of the couple interface x -----0, w h e n c o m -
p a r e d w i t h the free corrosion condition, Fig. 5 (b).
Experimental Test of the Numerical Solution
The analysis described above has been a p p l i e d to
a copper-zinc g a l v a n i c couple corroding in a 0.01M
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,
shown s c h e m a t i c a l l y in Fig. 6, comprises an open P e r -
spex vessel placed across the copper-zinc couple and
Electrometer
Microelectrode
filled w i t h solution to depths of 2 and 20 mrm T h e dis-
tribution of electrode p o t e n t i a l across the couple w a s
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)
(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
positioned using a m i c r o m a n i p u l a t o r . Distributions
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 -
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
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
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
to the s a t u r a t e d calomel electrode scale.
The polarization p a r a m e t e r s for zinc and copper in
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 -
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
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

Table I. Experimental values for the parameters used in the

O.01M HCL calculation of electrode potential distribution above the
copper-zinc corrosion couple in O.01M hydrochloric acid*

Zn Cu

Cu Zn .Anodic Tale] parameter, ,- (V) 0.025 0.001

Cathodic Tafel parameter, # (V) 0.05 0.05
-'-r- Corrosion current, i~ ( A m -~) 1.00 1.00
Free corrosion p o t e n t i a l , E (V SCE) --0.985 --0.845

Fig. 6. Schematic diagram showing the experimental arrangement

* Solution c o n d u c t i v i t y , C = 0.42 ~-~ m - l ; c a t h o d e w i d t h , a =
for measurement of electrode potential distribution above the 0.0075m; anode width, b = 0.02m; solution, d e p t h , w = 0.002 and
copper-zinc corrosion couple, 0.02m.

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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

0.95 -~ ~ 9 nnm mum mum

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 d i s t r i b u t i o n above the 20 m m depth example [Fig.
7 ( b ) ] is highly d e p e n d e n t on z. The very good agree-
m e n t observed b e t w e e n the m e a s u r e d and the cal-
culated electrode potential vs. x plots in Fig. 8 support
the accuracy a n d validity of this n u m e r i c a l analysis
procedure.
Discussion
The e x p e r i m e n t a l results show the present finite dif-
ference method of n u m e r i c a l analysis to be capable of
e v a l u a t i n g the distribution of electrode potential above
a coplanar galvanic corrosion couple i n which the elec-
trode reactions are subject to activation control. A p -
plication of such a n analysis requires an e x p e r i m e n t a l
d e t e r m i n a t i o n of the various electrochemical p a r a m -
eters describing the electrode reactions of each com-
p o n e n t of the couple, the value of a n y applied polariza-
tion, as well as the physical dimensions of the corro-
sion cell.
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The distribution of electrode potential for z > 0
w i t h i n the corrosion cell is i m p o r t a n t only insofar as it
is this which can be measured directly with a n ex-
t e r n a l reference electrode via a Luggin probe. This
volume distribution is a result of the electrode poten-
tial variation across the surface of the galvanic corro-
sion couple at z : 0. It is this latter distribution which
describes the kinetics and localization of the corrosion
reactions. Clearly, both the volume and associated sur-
face distributions of electrode potential are dependent
on all of the above electrochemical parameters and
physical dimensions (Fig. 4-8).
The distribution of electrode potential across a gal-
vanic corrosion couple describes the localization of the
corrosion reaction; consequently, a n y consideration of
corrosion behavior requires a knowledge of this dis-
tribution. The present analysis procedure allows this
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
polarization behavior from a n y combination of elec-
 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

Fig. 9. Computer analysis resuits for the corrosion couple de-

I I scribed in Fig. 4 showing the equipotential distribution for: (a,
-0.01 X" m 0.01 upper left) w = O.O01m, (b, upper right) w = 0.1m, and (c, lower
left) the electrode potential in solution vs. x a t z = O.

-0-2

w: 0.001
-0.4

trodes on w h i c h the reaction kinetics are subject to n u m e r i c a l m e t h o d of analysis is required. F i g u r e 9

activation control. The infinite n u m b e r of p e r m u t a t i o n s
of electrode polarization parameters, corrosion c u r -
rents, conductivity, and electrode dimensions w h i c h
can occur makes q u a n t i t a t i v e discussion of the separate
influence of each v a r i a b l e on the resulting electrode
potential distribution difficult. However, the q u a l i t a t i v e
effect of changes in each of these variables m a y be
predicted i n t u i t i v e l y and are not discussed f u r t h e r in
this paper.
Th e influence of changes in solution depth, w, h o w -
ever, is not so r ea d i ly envisaged. Clearly, for v e r y small
solution depths the e a r li e r a p p r o x i m a t i o n to u n i d i r e c -
tional c u r r e n t flow in the X direction remains valid
and p o t en t i al distributions m a y be obtained a n a l y t i -
cally (1, 2). However, for l a r g e r solution depths a
shows calculated results obtained using the s y m m e t r i -
cal model case shown in Fig. 4 for different values of
w = 1 and 100 mm. Figures 9(a) and (b) show the
eq u i p o t en t i al distribution w i t h i n the solution w i t h the
k,
Z axes adjusted for clarity of p r e s e n t a t i o n [c.f. Fig.
4(a) w i t h w = 10 m m ] . F i g u r e 9(c) shows the cal-
culated electrode potential vs. x at z = 0 for both
values of w. Clearly, the case for w = 1 m m [Fig.
9 (a) ] m a y be a p p r o x i m a t e d to a unidirectional curren~
f l o w i.e., all equipotentials are n e a r l y n o r m a l to the
electrode surface. F i g u r e 9 (b), w = 100 mm, however,
shows the case w h e r e w is l ar g e and the equipotentials
at z ~ w are p a r a l l e l to the electrode surface and t he
potential at z = w is almost constant. The m a i n point
of interest in these results, however, is the o b s e r v a t i o n

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 Vol. 126, No. 12 NUMERICAL ANALYSIS OF CORROSION
t h a t the absolute values and shape of t h e electrode p o -
t e n t i a l vs. x distributions at z = 0 a r e significantly
different for the two values of w [Fig. 9 ( c ) ] . This r e -
sults in a different d i s t r i b u t i o n of anodic dissolution
o v e r t h e anodic e l e m e n t B. S u c h an effect is of p a r -
t i c u l a r i n t e r e s t w h e n considering the r e l a t i v e c o r r o -
sion b e h a v i o r of galvanic couples u n d e r thin film a n d
b u l k solution environments. This m a y be of significance
w h e n a t t e m p t i n g to r e p r o d u c e service corrosion con-
ditions in s i m u l a t e d l a b o r a t o r y tests. P r e v i o u s a n a l y -
ses (1, 2) found the p a r a m e t e r (io/wC)l/2 to be of
f u n d a m e n t a l significance i n scaling distances o v e r
w h i c h p o t e n t i a l changes w e r e significant. Here, this
p a r a m e t e r has values of 10 and 1 VV2m-1 for w = 1
a n d 100 ram, respectively. Clearly, as the m a g n i t u d e of
this p a r a m e t e r increases the e a r l i e r a p p r o x i m a t i o n of
u n i d i r e c t i o n a l c u r r e n t flow becomes m o r e accurate.
S i m i l a r l y , changes in the electrode p o t e n t i a l d i s t r i -
b u t i o n above a corrosion couple r e s u l t i n g from an
e x t e r n a l l y a p p l i e d p o l a r i z a t i o n a r e not r e a d i l y p r e -
dicted. S u c h polarization is effected b y superimposing
a n a d d i t i o n a l e x t e r n a l c u r r e n t flow n o r m a l to t h e
surface of the corrosion couple. Changes in the
local c u r r e n t d e n s i t y at t h e electrode surface m u s t be
reflected in a shift in the electrode potential, Eq. [1]
a n d [2]. The a d d i t i o n a l c u r r e n t is s u p p l i e d b y some
e x t e r n a l source a n d is i n t r o d u c e d via an additional,
u s u a l l y inert, c o u n t e r e l e c t r o d e located r e m o t e from,
b u t u s u a l l y p a r a l l e l to, the surface of the corrosion
couple. I n the p r e s e n t analysis this position is defined
as the p l a n e z -- w and the electrode is p o l a r i z e d to
a constant p o t e n t i a l E~. W h e n E3 is fixed positive to
the n o r m a l free corrosion potential a net anodic c u r -
r e n t is d r a w n f r o m the corrosion couple which shifts
the electrode potential e v e r y w h e r e in the anodic d i r e c -
tion. S i m i l a r l y a n e g a t i v e v a l u e for E8 shifts the p o -
t e n t i a l d i s t r i b u t i o n in the cathodic direction. Thus, as
shown in Fig. 5 ( b ) , the r e l a t i v e d i s t r i b u t i o n of corro-
sion reactions is influenced b y an e x t e r n a l l y a p p l i e d
polarization. Such changes m a y be of f u n d a m e n t a l
i m p o r t a n c e w h e n considering e l e c t r o c h e m i c a l l y ac-
c e l e r a t e d test methods for assessing the localization of
corrosion in service components, e.g., crevice and p i t -
ting corrosion.
The p r e s e n t results c l e a r l y show -that t h e localized
corrosion b e h a v i o r of a galvanic corrosion couple is
d e p e n d e n t not o n l y on the various electrochemical
p a r a m e t e r s , b u t also on the corrosion cell g e o m e t r y
a n d the m a g n i t u d e of an e x t e r n a l l y a p p l i e d p o l a r i z a -
tion. The d e p e n d e n c e cannot be described a n a l y t i c a l l y
b u t m a y be e v a l u a t e d using the n u m e r i c a l finite dif-
ference p r o c e d u r e described above. The results to
d a t e indicate the need for caution in correlating local-
ized corrosion b e h a v i o r u n d e r different e n v i r o n m e n t a l
conditions.
Conclusions
1. The electrode p o t e n t i a l d i s t r i b u t i o n above a semi-
infinite, linear, coplanar, galvanic corrosion couple in
which the electrode reaction kinetics a r e s u b j e c t to
activation control m a y be e v a l u a t e d n u m e r i c a l l y using
finite difference methods.
2. The absolute values and distribution of electrode
p o t e n t i a l and associated corrosion b e h a v i o r a r e d e -
p e n d e n t not o n l y on the electrochemical p a r a m e t e r s
b u t also on t h e corrosion cell dimensions.
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2063
3. E x t e r n a l l y a p p l i e d polarization of a galvanic cor-
rosion couple preserves the o v e r - a l l form of the elec-
t r o d e p o t e n t i a l d i s t r i b u t i o n at t h e couple surface b u t
changes its precise shape a n d the r e l a t i v e absolute p o -
t e n t i a l values.
Acknowledgments
The authors wish to t h a n k Mr. F. A. J. F o r d a n d Mr.
A. J. Donovan (CEGB Computing Centre) for useful
discussions a n d Mr. G. D. Elson (CEGB C o m p u t i n g
Centre) for w r i t i n g the c o m p u t e r p r o g r a m used in
this work. This p a p e r is p u b l i s h e d w i t h the p e r m i s s i o n
of t h e Director General, C e n t r a l E l e c t r i c i t y G e n e r a t i n g
Board, S o u t h E a s t e r n Region.
M a n u s c r i p t s u b m i t t e d March 2, 1979; r e v i s e d m a n u -
script received J u n e 21, 1979.
A n y discussion of this p a p e r w i l l a p p e a r in a Dis-
cussion Section to be p u b l i s h e d in the J u n e 1980
JOURNAL. A l l discussions for the J u n e 1980 Discussion
Section should be s u b m i t t e d b y Feb. 1, 1980.
LIST O F S Y M B O L S
an Tafel p a r a m e t e r describing the anodic dissolu-
tion b e h a v i o r of e l e m e n t n (V)
;~n Tafel p a r a m e t e r describing the cathodic r e -
duction b e h a v i o r o~' e l e m e n t n (V)
C specific conductance of the solution ( a - i r a - l )
En the b u l k corrosion p o t e n t i a l of e l e m e n t n (V)
Ex the electrode potential at position x (V)
E~ the imposed e l e c t r o d e p o t e n t i a l at the b o u n d a r y
z = w (V)
io(n) the free corrosion c u r r e n t d e n s i t y on e l e m e n t
n (Am -s)
ia(x) the net anodic c u r r e n t d e n s i t y g e n e r a t e d o n
the anode at p o t e n t i a l Ex ( A m - s )
{c(x) the net cathodic c u r r e n t d e n s i t y g e n e r a t e d o n
the cathode at potential Ex ( A m -2)
w d e p t h of solution a b o v e t h e corrosion couple
surface (m)
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