PITTING BEHAVIOUR OF TYPE 316L S.

S IN
ARABIAN GULF SEAWATER1
Anees U Malik and Saleh A. Al-Fozan
ABSTRACT
An investigation has been canied out to evaluate the pitting corrosion behavior of AISI
316L in Arabian Gulf Seawater. The immersion test and electrochemical techniques were
utilized to study the different factors affecting the pitting corrosion. The influence of exposed
area on corrosion rate, CR and maximum pit depth, D can be expressed by lhe following
equations:

0.0082*A (0.512)

The maximum pit depth and exposure time also found to obey the following relationship:
D = 0.022 *t (0.136)
An increase in temperature causes a decrease in pittingpotential, and increase in corrosion
rate and pitting tendency. The activation energy of corrosion for 316L stainless steel in
Arabian gulf sea water as detennined from Arrhenius plots has been found to be -1324.7
cal/mol in the temperature range of 25oC to 9OoC. The kinetic of passive film formation
at corrosion potential of 316L stainless steel is slow, and the slow scan rate lets the film
thickening to occur, therefore, the slow scan rate is most suitable to study the localized
corrosion usingpotentiodynamic pitting test. The results show that more homogeneous is
the surface, higher the pitting potential and lesser the pit depth.
INTRODUCTION
The major cause of corrosion of passive materials is the breakdown of the protective
oxide film formed on the metal surface. Most common metals and alloys, however, are
susceptible to localized corrosion such as pitting and crevice corrosion in chloride
containing environments. The breakdown of passivity during crevice corrosion has been

1 Issued as Technical Report No. SWCC (RDC)-22 in October, 1992

792

attributed to reduced pH in the crevice [l], but with pitting there is, in general, no clearly
demonstrated cause of the initial breakdown 121. The breakdown of passivity, which
leads to localized corrosion is common type of failure in stainless steels.
Localized corrosion generally develops in conjunction with changes in the adjacent
aqueous environment which support rapid dissolution [3]. These changes are decisive
in determining whether the passive layer reforms or whether metal dissolution occurs,
especially with the more corrosion resistant alloys.
Pitting corrosion is one of the most destructive and insidious forms of corrosion because
of the localized nature of the attack and the difficulty associated with the prediction of
pitting tendency. Many investigations have been performed to understand the pitting
corrosion phenomenon. Recently, major efforts have been directed toward the characterization of pitting corrosion by the determination of two characteristic potential of
pitting, namely, pitting potential, and protection potential. In principle the pitting
potential (Ep) is the potential above which passive alloys are susceptible to pitting
corrosion in halide solutions, but below which pits can not be formed, although existing
pits can grow if the potential is greater than protection potential. The protection potential
(Epp) is the potential value such that at potential greater or equal to this potential, pit
can propagate, but if the potential is below, metal remains passive. For precise data,
the pitting potential can be determined only by recording the current density vs. time
relationship at various constant potential using a new sample for each curve. For precise
protection potential determination recording of the current density vs. time curve at
constant potential should be preceded by activation of the sample at high anodic potential
corresponding to easy pit nucleation. Measurements of changes in anodic potential at
constant current density starting from the corrosion potential; and measurement of
potential drop vs. time at high constant current density can be used [2]. Potentiodynamic
pitting test is the common technique for rapid evaluation of the relative pittingtendencies
of a series alloys. Both pitting potential and protection potential are the important
parameters from the theoretical point of view. For practical purpose, protection
potential is more useful because it indicates the range of potentials more negative than
protection potential within which pitting will not occur. Pitting potential depends on the
composition of the bulk solution, and on the surface condition of metal, while protection
potential depends upon the composition of the solution contained in pits.
Austenitic AISI 316L is considered to be one of the most resistant of common stainless
steels under marine environments, and it has good mechanical properties at elevated
temperatures, and easy fabricability, and therefore is an important structural material
for many industrial unit especially the desalination plants. The most common cause of
failure of 316L stainless steel in marine environment is pitting and crevice corrosion,
which are very dangerous, since the material can quickly be penetrated despite the fact
that its general corrosion rate is very low.

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Immersion and accelerated laboratory tests have been employed to study the resistance
and mechanism of localized corrosion of AISI 316L stainless steel in Arabian gulf
chlorinated sea water.
PREPARATION OF SPECIMENS AND GENERAL TESTS CONDITION
Commercially produced type 316L Stainless Steel sheet material of 3 m.m thickness
was used during tests. The composition of the material is given in table l.This material
was utilized for the studies of localized corrosion in Arabian gulf chlorinated sea water.
The composition of the sea water is given in Table 2.
i

Immersion Tests :

(a) Effect of Exposed Area In Pit Depth :

The test specimens were cut from 3m.m plate with 5.70 , 5.22, 10.02, 10.12, 14.56, 14.97,
19.07, 19.18, 35.06, 42.16, 54.36, and 54.45 cm2 in areas. The specimens were ground
with 240 grit SIC paper, degreased in acetone, rinsed with distilled water and were
immediately placed in the test container. The sea water used was at room temperature
(24 + 2oC). The test duration was three months. The experiments were done under
static condition.
(b) Effect of Exposure Time o n Pit Depth :
Rectangular test specimens were cut from 3 mm plate and were 40x20 mm in dimension.
The specimens were ground with 240 grit SiC paper, degreased in acetone, rinsed with
distilled water, and were immediately placed in the test container. The test durations
were 1,2,3 and 4 months, respectively. The experimens were carried out at room temperature and under static condition.
(c) Effect of Surface Finishing On Pit Depth :
Rectangular test specimens were cut from original sheet and were 40x20 mm in
dimension. The surface finishings were ground with 240 SIC paper, ground with 600 grit
Sic paper, and sand blasting. After surface finishing work, the specimens were degreased
in acetone, rinsed with distilled water, and were immediately placed in the test container.
Room temperature sea water was used. The test duration was three months. The
experiments were done under static condition.
(II) Electrochemical Tests :
Circular specimens with 16 mm diameter were punched from 3 mm plate. The exposed

794

area of the test specimens which was screwed in the sample holder was 1 cm2. The
specimens were ground with 600 grit SIC paper, degreased in acetone, rinsed with
distilled water, and were immediately placed in the test cell.
ELECTROCHEMICAL TEST PROCEDURE
The electrochemical technique was used to obtain pitting potential, protection potential,
and corrosion rate for AISI 316L under various conditions, using EG&G model 273
potentiostat/galvanostat with model 342 soft corrosion software. A saturated calomel
electrode was used as the referance electrode. Graphite electrodes were used as counter
electrodes.
The galvanostatic technique (potential vs time diagram) was used to obtain the anodic
potential as a function of time at constant current density, from which both pitting
potential and protection potential could be determined. The pitting potential value is
the highest value reached, and the protection potential is that value which remains
constant. The second method which was used to obtain the protection potential is the
measure of the decrease in potential with time at high as well as constant current density.
The protection potential value is that value which keep the potential constant with time.
The potentiostatic technique (current vs time diagram) was used to obtain the current
density as a function of time at constant potential. The pitting potential value is determined where the current density increases with time subject to pitting.
Potentiodymamic polarization was the third method which was used to study the pitting
behaviour, current density was measured by changing the potential continuosly at a
constant scan rate (0.17 mV/sec). The potential value at which the current density tends
to increase drastically is called pitting potential. The majority of the potentiodynamic
pitting tests were initiated at -250 mV vs corrosion potential, after stablizing for one
hour at the corrosion potential. The potential was scanned in the noble direction linearly
with the time at a scan rate of 0.17 mV/sec. This procedure was utilized to study the
effect of temperature, and effect of surface finishing on pitting potential. Two types of
test were employed in the studies of scan rate. In the first type test, the potential was
shifted in cathodic direction by -250 mV after keeping the specimen for two minutes at
the corrosion potential. The potential was scanned in noble direction linearly with time
at various rates (0.06, 0.1,0.17, 0.28, 1, 2,5 and 10 mV/sec). In the second type of test,
the potential was shifted in cathodic direction by -250 mV after keeping the specimen
for one hour at the corrosion potential. The potential was scanned in the noble direction
linearly with the time at various rates. In all the methods a new specimen was used for
each curve, and after each test the specimens were cleaned in distilled water, dried, and
were examined under an optical microscope. The linear polarization and tafel plottings
were used to calculate the corrosion rate under various conditions.

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RESULTS AND DISCUSSION

(I) Immersion Tests :
(a) Effect Of Exposed Area On Pit Depth :
Maximum pit depth was measured as a function of exposed area. The results of maximum
pit depth (mm) are listed in table (3),and are plotted as a function of exbosed area in
Figure l.The results show that the maximum pit depth increases as the exposure area
increases. The logarithmic relationship between maximum pit depth and exposure area
is evaluated in Figure 2.The mathematical equation which describes the relationship
from the linear plot between maximum pit depth and exposed area in Arabian gulf
chlorinated sea water is:
D

0.0082*A (0512)

Where:
D: The maximum pit depth (mm).
A: The exposed area (cm2).
The corrosion rates of specimens immersed in sea water and having different exposure
area were obtained. The corrosion rate data related to exposure area are listed in table
(3), and plotted as a function of exposed area in Figure (4). From the data plotted in
Figure (3) the corrosion rate of 316L stainless steel in gulf sea water can be expressed
by the following equation:
CR = 0.008 * A(0.089)
(b) Effect Of Exposure Time On Pit Depth :
The results of maximum pit depth as a function of exposure time are listed in table
(4),and plotted as a function of time in Figure (5).The results show that the pit depth
increases with increasing exposure time. The logarithm of maximum pit depth is linear
with logarithm of exposure time. Figure (6) shows that relation. The mathematical
equation which describes the relationship between maximum pit depth and exposure
time is represented as :
D = 0.022 * t

(0.136)

Where:
D is the maximum pit depth (mm).
t is the exposure time (month).

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The corrosion rates of 316L stainless steel exposed to sea water at different times were
obtained. The values of corrosion rate obtained at different exposure times are listed
in Table (4) and are plotted as a function of exposure time in Figure (7). The results
indicate that there is an initial increase in corrosion rate with increase in exposure time
(up to two months) which is followed by a decrease in corrosion rate with further increase
in exposure time.
(ii) Electrochemical Testing :
(a) Effect Of Test Techniques :
The pitting potential and protection potential were obtained from different techniques
(potentiodynamic, potentiostatic, and galvanostatic ). The results of pitting potential
and protection potential as a function of techniques are listed in Table (5) and plotted
in Figure (9). Figure (10) shows the variation of potential as a function of time at different
current densities applied. The curve which is obtained at current density of 1.61 has no
significant change in potential and the potential is lower than the protection potential
which means that no pit will be initiated at this current density. The appearnce of
maximum of the potential time curve at pitting potential is caused by competition
between two processes : pit nucleation and pit passivation. The vertex of the four curves
gives approximately the same value of potential which indicates that the pitting potential
would not be affected by applied current but it will effect the number of pits, and the
induction time of pit initiation. The values of induction time of pit initiation as a function
of applied current are listed in Table (6). Figure (11) shows the variation of current
density as a function of time. At a potential of 172 mV vs. SCE no change in current
density is abserved, but when the potential is increased by 0.1 mV, sharp change in
current density occurs which indicates pitting initiation at this potential. The figure also
shows a decrease in induction time of pit initiation with increasing applied potential.
Figure (8) shows the monitoring of the decreasing of potential with time after activating
the sample at high current density of 500 A, until the potential becomes constant which
indicates the protection potential. The values of pitting potential which are determined
from the current density vs. time relationship at various constant potentials would be
taken as exact values. The advantage of this procedure is that the measurement of each
sample is performed at only one definite potential. This excludes the phenomenon which
might occur at other potentials and affect the measurements.
(b) Effect Of Temperahire :
Pitting potential, protection potential, and corrosion rate measurements data were
obtained as a function of temperature. The measurements were done at 25,40,50,65,
and 90oC. The pitting potential, and protection potential (mV vs SCE) are listed in Table(7)
and plotted as a function of temperature in Figure (12). The results show a shift of
pitting potential to more active value as the temperature increases. The rate of shifting
to lower potential decreases with increasing temperature till it becomes contstant at

797

temperature above 65oC. This indicates that the pitting resistance of 316L stainless steel
decreases with increasing temperature. The influence of temperature on corrosion rate
has been shown in Figure (13) and the values are listed in Table (7).The kinetics of
chemical and electrochemical reactions are usually affected by the variations in temperature. According to Arrhenius equation the majority of the reactions proceed more
rapidly at higher temperatures. The Arrhenius plot is shown in Figure (14). The
relationship of logarithm of corrosion rate with the reciprocal of absolute temperature
is linear, and the slope of lines plot represents the activation energy which is -1275.6
Cal/mol in the temperature rang of 25 oC to 90 oC. The metallographic examination
shows heavy pit density at higher temperatures, but smallest pit depth; in other words
the process of pit nucleation at high temperatures is more unstable, and the current
distribution will be from large anode to small cathode affecting the pit depth. The typical
potentiodynamic and cyclic polarization curves are shown in Fig. 16 and Fig.17.
respectively at different temperatures.
(c) Efect Of Scan Rate :
Pitting potential was measured as a function of potential scan rate. The measurements
were done on two types of test. The pitting potential (mV vs SCE) of two test types are
listed in table (8), and are plotted as a function of potential scan rate for both types in
figures (17-a), and (17-b), respectively. The results in Figure (17-a) show that the pitting
potential increases in noble direction as the scan rate increases. The results in Fig17-b
show that the pitting potential shifts initially to the noble direction followed by
a shift in the active direction. A shift of pitting potential in the noble direction occurs
with two types of test at lower scan rates. This behavior is explained by incubation time
consideration. The short time allowed for film development by the second type test with
intermediate and rapid scan rates causes pitting at more active potential. The shifting
of pitting potential to active direction does not mean that the material is not resistance
to pitting corrosion. It only emphasizes that the kinetic of passive film formation is not
sufticicntly rapid to prevent premature breakdown of the film at intermediate or rapid
potential scan rates [5]. The typical potentiodynamic curves at different scan rates are
shown in Figure (18).
(d) Effect Of Surface Preparation :
The electrochemical tests were done with three types of surface finishings: grinding
with 600 grit SIC paper, sand blasting, and grinding with 600 grit SIC paper followed by
pickling in hot 50% nitric acid solution for 30 minutes. The immersion tests were carried
out also with three types of surface finishings: grinding with 240 SIC paper, grinding
with 600 grit SIC paper, and sand blasting. The values of pitting potential (mV vs SEC)
from electrochemical tests are listed in Table (9), and are plotted as a function of surface
finishing in Figure (19). The maximum pit depths as a function of surface finishing which
are obtained from immersion tests are listed in Table (l0), and have been plotted in
Figure (20). The results show that the pitting potential of specimen treated by HNO3 is

798

3.5 times higher than the pitting potential of the specimen ground by 600 SIC paper
indicating that the treatment by HNO3 will increase the resistance to pitting corrosion.
On the other hand, the pitting potential of specimen ground by 600 SIC paper is five
times higher than the pitting potential of the sand blasted specimen. The results shows
that more homogeneous is the surface higher the pitting potential and lesser the pit
depth. The treatment of specimens surface has its own beneficial effect to the pitting
potential. From the literature it appears that, the passiviation in HN03 has beneficial
effect. Sydberger [6] found that, the beneficial effect could be attributed to the removal
of sulfidic inclusions emerging on the surface, which were the sites for discrete pit
nucleation. As reported by Asami and Hashimoto [7], surface treatment appears to
affect the chromium content in the passive film. When the chromium content in the
surface film is large, both the pitting potential and corrosion potential are more noble.
The corrosion potential depends on the composition of the oxide film on steel. The film
protective ability and the steel composition do influence the pitting potential. The pitting
resistance is strongly affected by passive film quality; and the passive film quality is
strongly influenced by the type of surface preparation and the heat treatment.
CONCLUSION
(1) The maximum pit depth of 316L stainless steel in Arabian gulf chlorinated sea
water can be related to exposure area by the following equation:
D = 0.0082*A(0.512)
(2) The influence of exposure area on corrosion rate of 316L stainless steel can be
expressed by the following equation:

(3) The maximum pit depth of 316L stainless steel in gulf sea water can be expressed
by the following equation:

(4) The pitting potential varies for the same material under identical conditions
depending upon the technique which has been used.
(5) Pitting potential will decrease with increase in temperature, but corrosion rate and
pitting tendency will increase.
(6) The activation energy of 316L stainless steel in gulf sea water is -1324.7 cal/mol
in the temperature range of (25oC to 90o C ).

799

(7) The kinetic of passive film formation of type 316L stainless steel in gulf chlorinated
sea water is not fast enough.
(8) The slow scan rate will not be affected by minor variations in the experimental
procedure, and will let the film thickening to occur, therefore, the slow rate is the
best while using of the potentiodynamic pitting test to study the localized corrosion.
(9) Pitting potential of 316LS.S specimens treated withHNO3, is about 3.5 times higher
than the specimens ground by 600 SIC paper and about 17.5 times higher than the
sand blasted specimens.
(10) Corrosion rate of 316L S.S in sea water is lowest (0.0061 mpy) for HNO3 treated
specimen being about one order of magnitude lower than sand blasted specimen
and about 3 times lower than 600 SIC finished specimen.
(11) More homogeneous is the surface of steel specimen, higher will be the pitting
potential and lesser the pit depth.
REFERENCES
(1)
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Z. Szklarska, Smialowska, Pitting Corrosion of Metals, NACE, Houston, 1986.
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P.E. Manning, D.J. Duquette, and W.F. Savge, corrosion,36,313, 1980, NACE.
P.E. Manning, Corrosion, 36, 468, 1980, NACE.
T. Sydberger, Werkest, Korros, 32,119,1981.
K. Asami, K. Hashimoto, Corros. Sci., 19,1007, 1979.
R. J. Brigham and E.W. Tozer, Corrosion, 29,33,1973, NACE.
R. Bandy and D. Van Rooyen, Corrosion/82, paper number 71, NACE, 1982.
H.H. Lu and D.J. Duquette, Corrosion, 46,994,1990, NACE.
R.K. Dayal, N. Parvathavarthini, and J.B. Gnanamoorthy, Corrosion, 36,433,1980,
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(12) M.H. Cotterrell, R.E.J. Noel, and C. Allen, Br. Corros. J, 2560, 1990.
(13) R. Guo, and M.B. Ives, Corrosion, 46,125,1990, NACE.

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