Corrosion Science, Vol. 33, No. 11, pp.

1809-1827, 1992

0010--938X/92$5.00 + 0.00
~ 1992 Pergamon PressLtd

Printed in Great Britain.

THE INFLUENCE OF pH A N D CHLORIDE

CONCENTRATION ON THE CORROSION B E H A V I O U R
OF AISI 316L STEEL IN A Q U E O U S SOLUTIONS
A . U. MALIK, P. C. MAYAN KUTTY, NADEEM A . SIDDIQI, ISMAEEL N. ANDIJANI a n d

SHAHREERAHMED
Research Development and Training Center, Saline Water Conversion Corporation (SWCC),
P.O. Box 8034, A1-Jubail-31951, Kingdom of Saudi Arabia
Abstract--The effect of chloride concentration, pH, dissolved oxygen and temperature on the pitting
behaviour of 316L SS in aqueous solutions has been investigated under dynamic and static conditions.
Weight loss, metallography and electrochemical polarization techniques have been employed during the
investigation. It has been found that the corrosion rate generally increases linearly with increasing CI
concentration in the range 100-5000 ppm. With increasing pH, the corrosion rate decreases, being highest
at pH 4 and lowest at pH 9. The number and depth of pits increase with increasing CI concentration.
From the results of cyclic polarization studies it is inferred that the pitting potential, Epit is shifted to a
more negative potential with increasing CI- concentration and temperature and decreasing pH. It has
been established that low pH, high CI- content and stagnancy are the conditions most suitable for
initiation and propagation of pitting in A1SI 316L stainless steel.
INTRODUCTION
PITTING is a l o c a l i z e d c o r r o s i o n a t t a c k on m e t a l s a n d alloys in a q u e o u s e n v i r o n m e n t s .
It is a m a j o r cause o f failure o f c h e m i c a l p r o c e s s i n g a n d d e s a l i n a t i o n p l a n t s , w a t e r
s t o r a g e t a n k s a n d p i p e lines, p u m p s a n d valves, p e t r o l e u m refineries etc. D u e to t h e
l o c a l i z e d n a t u r e of p i t t i n g c o r r o s i o n , the f o r m a t i o n o f pits is c o n f i n e d to m u c h s m a l l e r
a r e a s c o m p a r e d to the o v e r a l l e x p o s e d surface. B r o a d l y s p e a k i n g , t h e initiation o f
pitting is the result of t h e b r e a k d o w n o f the passive film on the m e t a l d u e to the
p r e s e n c e o f c e r t a i n a n i o n s such as C1- a n d the s u b s e q u e n t e s t a b l i s h m e n t o f an
e l e c t r o c h e m i c a l cell in which t h e d a m a g e d site acts as an a n o d e a n d the passive site
acts as a c a t h o d e . T h e b u i l d i n g up o f c o r r o s i o n p r o d u c t s on t h e m o u t h o f the pit m a y
result in t h e f o r m a t i o n o f a crevice, thus p r o d u c i n g m o r e aggressive c o r r o s i o n a t t a c k .
I r o n - b a s e alloys, p a r t i c u l a r l y a u s t e n i t i c stainless steels, a r e m o s t p r o n e to p i t t i n g in
d i s s o l v e d CO2- a n d C l - - c o n t a i n i n g e n v i r o n m e n t s such as t h o s e o b s e r v e d in b r i n e
recycle a n d b l o w d o w n p u m p s , flash c h a m b e r s a n d d e m i s t e r s o f d e s a l i n a t i o n p l a n t s ,
a n d in s t e a m b o i l e r s , f e e d w a t e r h e a d e r t u b e s a n d s t e a m t u r b i n e b l a d e s o f p o w e r
plants. 1-5
T h e effect of c h l o r i d e on the pitting s u s c e p t i b i l i t y o f v a r i o u s m e t a l s a n d alloys a n d
e s p e c i a l l y stainless steels has b e e n e x t e n s i v e l y i n v e s t i g a t e d by n u m e r o u s r e s e a r c h e r s
a n d is r e v i e w e d in a n u m b e r o f b o o k s , reviews a n d articles. 6-~3 P a r t i c u l a r i n t e r e s t has
b e e n s h o w n for the C I - d u e to its p r e s e n c e in sea w a t e r as t h e m a j o r c o n s t i t u e n t a n d
its role as an active p i t t i n g a g e n t . B e s i d e s t h e influence o f t e m p e r a t u r e , flow velocity,
p H a n d C I - c o n c e n t r a t i o n [ C I - ] on pitting, the synergic effect of a n i o n s such as
S O ] - , $2032-, C 1 0 4 etc. h a v e also b e e n s t u d i e d . S m i a l o w s k a 14 f o u n d t h a t a m a j o r i t y
Manuscript received 25 September 1991.
1809

1810

A . U . MALIK et al.

of construction materials suffer pitting only in solutions containing Ci- or other

halide ions. Three main reasons are given for the specific effects of chloride and its
ability to produce pitting. Firstly, the formation of a chloride complex with cation
and hydroxide; secondly, an increase of hydrogen ion activity in the pit electrolyte
and thirdly, the formation of a salt layer at the bottom of pits. The third factor
appears to explain more specifically the role of halides in pitting attack. It is
suggested that transition from passivity to pitting conditions can be explained by a
competitive adsorption mechanism in which chloride ions move into the double layer
(oxide/liquid interface), eventually reaching, at a critical potential, Emit, corresponding to the [CI-] required to displace the adsorbed oxygen species. ~5-f?, Nashimura et
al. 17-18 found that pit initiation is strongly related to two different types of bound
water in a film. It was found that the pitting behaviour of alloys covered with the
passive film is largely dependent on the film thickness and ion selectivity. During
studies 19 on the effects of [CI-] on pitting behaviour of steels linear relationships
have been found to exist between pit nucleation potential vs log chloride ion
concentration, and log induction time vs log chloride ion concentration. The
temperature appears to be an important parameter in influencing the protectivity of
the oxide scales.
AISI 316L is considered to be one of the most important of stainless steels for
marine environments and therefore is widely used as a structural material for
desalination plants. Even this alloy may fail under conditions of low pH, high
chloride content or stagnation. 8"2-21 Relatively few studies have been carried out to
investigate the role of pH and stagnancy on the pitting behaviour of austenitic steels.
The present communication contains the results of a study emphasizing the role of
pH, chloride ion concentration, stagnancy and temperature on the pitting behaviour
of AISI 316L austenitic stainless steel in aqueous chloride solutions.
EXPERIMENTAL

METHOD

Commercial grade AISI 316L stainless steel (17.1 Cr, 11.3 Ni, 2.1 Mo, 0.02 C and balance Fe, all in
wt%), in sheet and rod forms, was used for the studies.
For immersion tests, coupons of about 5 cm 2 area were cut from the sheet and abraded sequentially
with 180, 320,400 and 600 grit SiC papers. The abraded specimens were cleaned in an ultrasonic cleaner
followed by drying. The dried specimens were weighed prior to immersion.
For electrochemical measurements, circular flat test specimens of 1.5-1.6 cm diameter were used. The
exposed area of the test specimens which was screwed in the sample holder was 1 cm2 . Electrochemical
polarization studies were carried out on an E G & G model 342-2 soft Corr measurement system. The
system was consisted of model 273 potentiostat/galvanostat, model 342 Corr software and model 30 IBM
PS-2. All the experiments were carried out using a corrosion cell (EG & G model K0047) with saturated
calomel and graphite as reference and counter electrodes, respectively. Several series of experiments were
carried out in order to study the effect of [CI-], pH and stagnancy on the pitting behaviour of AISI: 316L
steel using test solutions under following conditions:

pH
[CI I (ppm)
Artificial sea water
Immersion time (weeks)
Condition
Temperature
Dissolved oxygen (ppm)

4, 7 and 9
0, 10,100,300,500, 1000 and 5000
CI 24150 ppm
4, 8, 16 and 24
Static or dynamic
20 , 25 , 30 , 50 and 80 (2C)
60.5

pH and [CI-] and the corrosion of AISI 316L steel

1811

Previously weighed coupons were immersed in test solutions for various time intervals of 1,2, 4 and 6
months. Immersion tests under static conditions were performed following the ASTM G31-72 procedure.
Similar tests were carried out under dynamic conditions using a thermostatic shaker moving at a speed of
60 oscillations min - 1. At the end of the test periods the coupons were taken out, washed in distilled water,
dried and their weights were dctermincd.
Following the immersion test, microstructural examination of all the test specimens was carried out to
assess the nature and extent of the localized attack. The shape, size and density (distribution) of the pits
were determined metallographically using an optional microscope and following ASTM G46-76 procedure.
Open circuit potential (OCP) were measured using 316L coupon as a working electrode (WE) and
saturated calomel (below 80C) or silver-silver chloride as a reference electrode. The OCP studies wcrc
carried out with 100, 300, 500, 1000 and 5(100 ppm chloride solutions of pH 4, 7 or 9 and at different
temperatures. It took 24-48 h to achieve a constant potential corresponding to open circuit corrosion
potential.
Potentiodynamic polarization experiments were carried out using a scan rate of 0.1 mV s i
commencing at a potential about 250 mV more active than the stable OCP. Before starting the
polarization scan, the specimen in the sample holder (WE) was left in the cell for about 1 h to attain a
steady state which is shown by a constant potential and current at the beginning of the experiment. Thc
potcntiodynamic runs were programmed such that upon attaining a current density of 25/tA cm 2, the
scan direction was reversed and the potentials were scanned back to the starting potential.
Polarization resistance measurements were conducted at a scan rate of 0.1 mV s ~ with starting and
final potentials corresponding to -20 and +21) mV (OCP), respectively. The maximum current range was
0.1/Acm 2.
EXPERIMENTAL

RESULTS

Weight loss studies

W e i g h t loss s t u d i e s s h o w e d t h a t n o p e r c e p t i b l e w e i g h t loss o c c u r s d u r i n g
i m m e r s i o n p e r i o d s o f up to 6 w e e k s i r r e s p e c t i v e o f [C1-], p H a n d d y n a m i c o r static
c o n d i t i o n s . E x t r e m e l y l o w w e i g h t losses ( 5 0 - 7 0 ktg c m 2) w e r e n o t e d d u r i n g
i m m e r s i o n t i m e v a r y i n g f r o m 16 to 24 w e e k s . T h e w e i g h t losses r e c o r d e d w e r e
h i g h e s t at p H 4 u n d e r static c o n d i t i o n s a n d w e r e l o w e s t at p H 7 u n d e r d y n a m i c
conditions.

Metallographic examinations
U n d e r s i m i l a r c o n d i t i o n s , a m a x i m u m n u m b e r o f pits w e r e f o u n d o n t h e
s p e c i m e n s i m m e r s e d in s o l u t i o n s o f p H 4 a n d a m i n i m u m o n s p e c i m e n s i m m e r s e d in
s o l u t i o n s o f p H 7. U n d e r d y n a m i c c o n d i t i o n s ( w h e n t h e s o l u t i o n s w e r e a g i t a t e d
c o n t i n u o u s l y d u r i n g t h e e n t i r e p e r i o d s o f i m m e r s i o n test) t h e n u m b e r o f pits
o b s e r v e d o n t h e s u r f a c e o f t h e s p e c i m e n was s m a l l e r t h a n u n d e r static o r s t a g n a n t
c o n d i t i o n s . In g e n e r a l , t h e n u m b e r a n d d e p t h o f t h e pits i n c r e a s e d w i t h i n c r e a s i n g
[CI ] a n d i m m e r s i o n t i m e .

Pit depth measurements

T h e d e p t h o f t h e pits o n 3 1 6 L s p e c i m e n s was m e a s u r e d m i c r o s c o p i c a l l y . M i n i m u m a n d m a x i m u m pit d e p t h s w e r e m e a s u r e d f o r a p a r t i c u l a r s p e c i m e n . A v e r a g e
d e p t h s w e r e d e t e r m i n e d by c o n s i d e r i n g t h e d e p t h o f all t h e pits p r e s e n t . F i g u r e 1
s h o w s p l o t s o f m a x i m u m pit d e p t h vs [C1 ] a n d d i f f e r i n g p H f o r t h e i m m e r s i o n p e r i o d
o f 4 m o n t h s . T h e pit d e p t h i n c r e a s e s w i t h i n c r e a s i n g [CI ]. A p a r a b o l i c r e l a t i o n s h i p
a p p e a r s to exist b e t w e e n pit d e p t h a n d c h l o r i d e c o n c e n t r a t i o n as i n d i c a t e d by t h e
l i n e a r n a t u r e o f pit d e p t h vs [C1 ]1/2 p l o t s (Fig. 2).

1812

A.U.

5oo

MALIK et al.

o pH 4S
0 pH 7S

300

t
_

o pH 9S

b
~

cL 200

o
IO0

~
40

I
80

I
120
CI-

F[c. 1.

I
160

I
200

I
Z40

I
280

(ppm)

M a x i m i m pit depth vs [C1-] f o r A I S I 316L in C l - - c o n t a i n i n g aqueous solution of

various pH values under static(S) and dynamic(D) conditions. Immersion time: 4 months.

Figures 3 and 4 show typical optical micrographs of the pits produced by

potentiodynamic anodic polarization at two different [CI-]. Most of the pits are
generally of small diameter (<50 ~m).
Electrochemical measurements
Open circuit corrosion potential. Figures 5-7 show some typical time vs open
circuit potential plots for 316L steel immersed in aqueous solutions containing
varying [C1-] at pH 4, 7 and 9, and at 30 , 50 and 80C. The induction time, ti, for pit

500
[] Stotic

300

"o

2OO

0
3

I
5

I
7'

I
9

I
11
1

I
13

I
15

I
17

[cl-]~
Fro. 2.

Plot of [ E l - ] 1/2 vs m a x i m u m pit depth for A I S I 3 1 6 L immersed in Cl- -containing

solutions of p H 4 under static(S) and dynamic(D) conditions.

FIG. 3.

Photomicrograph of a cross section of AISI 316L specimen pitted potentiodynamically ([CI ]: 5000 ppm, pH 4). x400.

FIG. 4.

Photomicrograph of a cross section of AISI 316L specimen pitted potcntiodynamically ([C1 ]: 1000 ppm, pH 7, under de-aerated condition). )<400.

1813

1815

pH and [ C I - ] and the corrosion of A1SI 316L steel

200

100

E
o

"5
(3-100

-2oo

300
500

~.

1000

~
0

12

L _ _ _ i _ _ J . _ _ ~
20
24
23
32
36
40
44

16

Time

FIG. 5.

48

(h)

Variation of OCP with time for AISI 316L immersed in aqueous solutions of
varying [CI-] (in ppm) at 20C (pH 4).

initiation has been determined from the plots. At any given temperature, ti is a linear
function of [CI-] and can be represented by the relationship:
log ti = C + D log [CI-].
Both C and D coefficients are temperature dependent. Figure 8 shows plots for
log induction time for pit initiation vs log [CI-] at pH 4 and at different temperatures.
Figure 9 shows plots of log induction time vs temperature at two [Cl-] concentrations. The plots indicate that induction time for pit initiation, ti decreases with
increasing [CI-l] and increasing temperature.

40

O'

40

"6

[J 30 C

-80

,,, 50oc
o 80C

-120

- 160

2
0

0
8

12

0
16

20
Time

F1o. 6.

.
24

28

~
32

36

40

44

48

(h )

Variation of OCP with time for AISI 316L immersed in 1000 ppm [C1- ] aqueous
solutions at various temperatures (pH 4).

1816

A . U . MALIK etal.
8O

-_
/

o .4

~T

o pH 9

- 200

12

16

20

24

28

32

36

40

44

48

Time (h)
V a r i a t i o n o f O C P with time for A [ S [ 3 1 6 L immersed in 1000 ppm C I - aqueous

FIG. 7.

solutions of different

pH values at 20C.

Polarization resistance. Polarization measurements were carried out using 316L

coupons immersed in chloride-containing aqueous solutions under conditions of
varying temperature, pH and [CI-]. Typical polarization resistance plots are shown
in Figs 10-12. Table 1 lists the corrosion rate values computed from the plots. The
corrosion rate values as determined from the polarization resistance experiments
were based on anodic and cathodic Tafel values which were obtained from previously
carried out Tafel plot runs. The polarization data provide the following information
regarding the behavior of 316L in chloride-containing solutions: (i) at pH 4, the

2.0
i.8
1.6
1.4
12
"~-

1.0

[] 30 C
z~ 5 0 C

...I Q8

o 80 c

0.6
0.4
Q2

I
1

I
2

I
3

Log CI -

FIG. 8.

Log induction time for pit initiation vs log [CI-] at various temperatures (pH 4).

pH and [C1-] and the corrosion of AISI 316L steel

1817

2.0
1.8
1.6

1.4

1.2 1.0

.J
0 . 8 -

1 0 0 0 ppm

0.6-0.4 -0.2--

I
20

01
0

I
4O

I
60

Tempereture
FIG. 9.

I
80

100

(C)

Log induction t i m e r or pit initiation vs temperaturc at 100 and 1000 p p m [ C t

(pH4).

TABLE 1. RESULTS FROM POLARIZATION RESISTANCE MEASUREMENTS

Temp
C
20
20
20
20
20
30
5(1
80
20
30
50
80
20
30
50
8(1
25
20
20
20

[Cl ]
ppm

pH

E .....
mV

Corrosion rate
MPY

100
300
500
100(I
5000
1000
1000
1000
1000
1000
1000
1000
1000
1000
1000
1000
24153*
1000t
1000t
1000+

4
4
4
4
4
4
4
4
7
7
7
7
9
9
9
9
7.3
4
7
9

-156
-120
-144
-168
-185
-203
-127
-93
-50
-150
-122
-200
-231
-219
-238
- 287
-249
-343
-235
-238

0.104
0.116
0.119
0.135
0.148
0.143
0.154
0.295
0.071
0.051
0.03
0.169
0.011
0.041
0.(155
0.163
0.064
0.049
0.041
0.010

* Artificial sea water.

t De-aerated.

A . U . MALIK etal.

1818

-145
100 p p m
-156
1000 ppm
-167
.r,

-178

5000 ppm

-189

- 200
- 0.060

'
- 0.028

-0.044

FIG. 10.

'
- 0.012

,
0.004

(/cA m - 2 )

P o l a r i z a t i o n resistance curves f o r A I S i

3 1 6 L in a q u e o u s s o l u t i o n s o f v a r i o u s

c h l o r i d e c o n c e n t r a t i o n s at p H 4 a n d 20C.

-85

80~C

-110
.:

50. C

:...-,

-135

....

E
uJ

20=C

--160

30C

-18!

r ~
-21(
-0.10

l
-0.06

i
-0.02

i
0.02

I
0.06

I ( # A c m -2 )

FIG.

II.

P o l a r i z a t i o n resistance curves f o r A I S [ 3 1 6 L in 1000 p p m C I - solutions o f p H 4

and at different temperatures

pH and [ C I - ] and the corrosion of AISI 316L steel

1819

145

pH 7
1

-163

181

199

E
w

pH 4

-217
pH 9

-235
-0030

~
-0.014

- 0.022

FIG. 12.

i
- 0.006

0,002

(#,Am- 2 )

Polarization resistance curves for AISI 316L in 1000 ppm C l - solutions of various
pH values at 30C.

0.16

0.15

0.14

0.13

0.12

0.11

A
E

,8
o
(.~

.11. 4

1.8

2,2

2.G
Log

Fro. 13.

I
3.0

3,4

3,8

Cl-

Corrosion rate vs log [CI-] at 20C and pH 4.

820

A . U . MALIK et al.

0.30
0.26

13 p H 4
,a, pH 9

A
>, 0.22

E
0.18
o
0.14.

L_

0.10

g,

zx

0.06

/x
0.02

~,

20

40

60

80

Tempereture
FIG. 14.

100

(C)

C o r r o s i o n rate vs t e m p e r a t u r e at 20C and p H v a l u e s 4 and 9.

900

'"""1

'"'""I

'"'""1

'"'"'~

600

........

' '~ ....

',

30O

>
2

,,,

.-"

.............
-

-_~."

300

10-3

10-2

10-1

100

101

102

103

I (/~A cm-2)
F1G. 15.

Cyclic p o l a r i z a t i o n curve for A I S I 316L in 100 p p m CI - s o l u t i o n of p H 4 at 30(

pH and [ C I - ] and the corrosion of AISI 316L steel

'"i'",l

600

'"i'"'l

'"i'"'l

'"1'"9

'"i'"'

182

"l'

400
7
J

200

E
U.I

- 200

-400

,,
10-3

;,
10-2

, ,l<,:A
......
10-1

[
100

I (/~A
FIG. 16.

, ~ll

, ,,,
102

101

,
103

cm -2)

Cyclic polarization curve for AIS1316L in 1000 ppm CI - solution of pH 4 at 30C.

150

.Z-

50

"

-i

ar -'"

- 50
c

E
W

-150

"---

-250

-35o

......
10-2

J
10-1

.....

i
100

.,,i
101

102

I (/.LA cm-2)
FI~. 17.

Cyclic polarization curve for AIS! 316L in 1000 ppm CI solution of pH 4 at 80C.

1822

A . U . MALIK et al.
TABLE 2. RESULTS FROMCYCLICPOLARIZATIONSTUDIES

Temp

[Cl-]

ppm

20
20
20
20
20
30
50
80
20
30
50
80
20
30
50
80
25
20
20
20
20

100
300
500
1000
5000
1000
1000
1000
1000
1000
1000
1000
1000
1000
1000
1000
24153*
1000t
1000t
1000t
24153*

pH

4
4
4
4
4
4
4
4
7
7
7
7
9
9
9
9
7.3
4
7
9
7.3

gpi t

gprot Epit-gprot

mV

mV

mV

Er
mV

759
502
438
425
322
260
177
-4
217
294
234
111
862
611
389
467
304
504
427
814
304

-199
-82
-100
-77
-140
-62
-29
-38
-49
-4
-48
-27
-186
-279
-273
-375
-230
-79
-107
-216
-230

958
584
538
502
462
322
206
34
266
298
282
138
1058
990
662
842
534
578
634
1030
534

-300
280
250
200
67
20
0
233
66
82
133
-----200
87.5
67
75

* Artificial sea water.

t De-aerated.

corrosion rate generally increases linearly with increasing [CI-] in the range
100-5000 ppm (Fig. 13); (ii) with increasing pH, the corrosion rate decreases, being
highest at pH 4. The rates at pH 7 and 9 are similar in magnitude; (iii) in general,
corrosion rate increases with increasing temperature being highest at 80C and
lowest at 30C (Fig. 14).

Cyclic polarization. Some representative cyclic polarization curves for 316L in

Cl--containing solutions are shown in Figs 15-17. A hysteresis loop is traced during
reverse scan indicating the possibility of pitting. Table 2 lists the values of pitting
potential (Epit) and protection potential (Eprot), which are defined as the potential
where the forward and reverse scans cross. Repassivating pitting potential (Er) is
also considered, which is defined as the most active potential at which the nucleation
of unstable (i.e. repassivating) pits can occur and is characterized by a reversible
increase in current density (CD). The stable nucleation potential (Epit) is assessed as
that at which a consistent increase in CD occurs, indicating the initiation of nonrepassivating pits. Eprot is the most active potential at which pit propagation can
Occur.

In general, pitting potential, Epit is shifted to a more negative (or active) value
with increasing [CI-] or temperature.
At a particular temperature and [CI-] Epi t shifts to a more noble potential with
increasing pH. The electrochemically measured pit potential, Epi t is found to be a

pH and [C1-] and the corrosion of AISI 316L steel

1823

900

800
70O

60O
E

500

~ 4oo
3OO
200
100

4
Log C I -

FIG. 18.

(ppm)

Pitting potential vs log [C1-] at 20C and pH 4.

linear function of the logarithm of [CI-] (Fig. 18). This linear dependence of Epi t o n
log [C1-] can be represented as:
gpi t = A + B

log [C1-].

Both the A and B coefficients are temperature dependent. Figure 19 shows the
dependence of Epi t o n temperature at different values of pH at a fixed [Cl-]. A shift
of E pit in the negative direction usually occurs as the temperature increases.

900
oo

700

600

[] pH 4
pH7

500

o pH 9

4O0

t.u
2OO
100
0
-100
o

I
20

I
40

Tempereture
FIG. 19.

I
60

I
80

~oo

(C)

Pitting potential vs temperature for AISI 316L in 1000 p p m CI

various pH values at 30C.

solution of

1824

A . U . MALIK et al.
DISCUSSION

The immersion tests carried out on 316L coupons at different [C1-] concentrations, pH and time intervals and under static and dynamic conditions show extremely
low weight losses (10-50/~g in typical 4-month runs). At a particular chloride
concentration and immersion time, the weight losses were more or less independent
of pH and immersion conditions (static or dynamic). The number and depth of the
pits increase with increasing immersion time. The maximum number of pits were
found on specimens immersed in solutions of pH 4. At pH 7 and 9, the pits were
generally shallow and the number was smaller, though some of them were deep.
Under dynamic conditions, the number of pits observed on the surface of the
specimen was much smaller than under stagnant conditions.
In the presence of Cl-, austenitic stainless steels are subjected to local attack in
the form of pitting or crevice corrosion due to breakdown of the protective Cr20 3
film at random sites. 6 The pitting on the passive surface has been explained by the
competitive adsorption mechanism 15'16in which chloride ions move into metal/oxide
film interface at the metal surface. At a particular chloride concentration, a critical
potential (Epit) develops which is sufficient to displace oxygen from the protective
oxide layer. It appears from the present study that the low pH and stagnancy would
provide most favourable conditions for pit growth. In a typical case, at 30C and 4-5
ppm dissolved oxygen, the pits grow to maxima of 450 and 325 #m at pH 4 under
static and dynamic conditions, respectively, when 316L specimens were immersed in
300 ppm chloride solutions for 4 months. At higher pH values (7 and 9) the depth
rarely exceeded 70/~m. The pit depth has been found to be a parabolic function of
CI- concentration and therefore, with increasing [C1-] the rate of pit growth appears
to slow down.
The electrochemical studies on pitting corrosion were carried out at pH values of
4, 7 and 9. At a particular [C1-] and a given temperature, the corrosion rates were

320
300
280

260
I:: 24O
I,~ 220
200
180
160
0

4
Log C l -

FIG. 20.

(ppm)

Repassivating potential vs log [C1-] for AISI 316L in aqueous solution of pH 4

and at 20C.

pH and [ C l - ] and the corrosion of AISI 316L steel

1825

900

800

700

600

uj~ 500
4OO
30O
2O0
20

22

24

26

ti

Flo. 21.

Pitting potential vs induction time for pit initiation in 1000 ppm CI solution o f p H
4 and at 20C.

found to be highest at pH 4 and lowest at pH 9. Considering the effect of pH on

pitting potential, Epi, the potential was found to be shifting to more positive values
with increasing pH. The corrosion rate of 316L in artificial sea water ([C1-] 24153
ppm and pH = 7.3) was similar to that in 1000 ppm CI- solutions of pH 7 and 9 but
much lower than that in a solution of pH 4 of the same concentration. The effect of
chloride concentration on the stable pit nucleation potential, Epi t is consistent with
that observed with other systems whereby the potential varies linearly with the
logarithm of Cl- activity. Leckie and Uhlig 15 reported a 88 mV shift in the critical
nucleation potential by a 10-fold increase in CI- activity in the concentration range
0.01-1 M (350-35,000 ppm). In the present study a shift of about 200-300 mV was
observed by a similar increase in the concentration range 100-5000 ppm at pH 4. The
repassivating potential, Er also varies linearly with the logarithm of the concentration of chloride (Fig. 20). However, no systematic variation in protective
potential, Eprot , was found. At [Cl-] levels of 100 ppm or below no repassivating
potential was observed. The induction time, ti, for pit initiation measured under
open circuit conditions has been found to be a linear function of pitting potential,
Epit, and follows the relationship:
Epi t = A + B log ti
where A and B are temperature dependent coefficients (Fig. 21).
At [C1-] concentrations at which stable nucleation was evident (100-30,000 ppm)
extensive hysteresis was observed upon scan reversal with repassivation occurring in
the vicinity of the OCP. The pitting potential, g p i t , w a s invariably more positive than
the protective potential, Eprot. The difference between pitting and protective
potentials decreases with increasing [CI-] and is a linear function of logarithm of
[C1-] (Fig. 22). The occurrence of pit initiation potentials in the transpassive range
can be explained in terms of the localized breakdown of a surface film on 316L that is

1826

A.U. MALIKet al.

640

600

560
520
I

"~ 4 8 0

440

400
0

Log CI-

(pprn)

FIG. 22. Difference of pitting potential and protective potential vs log [CI-] at 20C and
pH 4.

somewhat less protective (i.e. shows a higher rate of general dissolution) than that
prevalent in the passive region. At p H 4, under similar conditions of temperature and
[Cl-], the repassivating potential, Er, appears at a much higher positive potential
than at pH 7. No repassivating potential was observed at pH 9. It leads to the
conclusion that at p H 4, the nucleation of repassivating pits occurs at overpotentials
far below that required for stable pitting; resulting thereby in the onset of a dynamic
process of pit initiation and repassivation prior to the development of propagating
pits.
CONCLUSION
The pitting behaviour of AISI 316L in chloride-containing solutions is greatly
influenced by the variation in [C1-], pH, dissolved oxygen, temperature and flow
conditions. The electrochemical polarization experiments carried out show that the
corrosion rate, pitting potential, Epit, and repassivating potential, Er, are linear
functions of [Cl-]. The induction time, ti, measured under open circuit conditions,
has also been found to be a linear function of pitting potential, Epi t.
An analysis of the experimental results indicates that in general, low pH, high
[Cl-] and stagnancy are the most favourable conditions for initiation and propagation of pits in AISI 316L steel.
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1827

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