Materials Chemistry and Physics 63 (2000) 67–74

The effect of some sulphur compounds on the pitting corrosion of

type 304 stainless steel
E.A. Abd El Meguid a,∗ , N.A. Mahmoud a , S.S. Abd El Rehim b
a Electrochemistry and Corrosion Department, National Research Centre Dokki, Cairo, Egypt
b Department of Chemistry, Faculty of Science, Am Shams University, Cairo, Egypt

Received 20 April 1999; received in revised form 10 August 1999; accepted 19 August 1999

Abstract
The potentiodynamic anodic polarization behaviour of AISI 304 stainless steel (SS) in 0.1 M NaCl containing various concentrations
of SO4 2− , SO3 2− , S2− SCN− or S2 O3 2− anions has been studied. In pure chloride solutions, the alloy exhibited pitting corrosion. The
addition of low concentrations of the sulphur containing anions (except SO4 2− ) decreases the pitting potential. The sulphate anion appears
to increase the pitting potential. The electric charges associated with the pitting initiation and propagation processes were calculated when
the steel was immersed under potentiostatic potential of +320 mV for 10 min in 0.1 M NaCl without and with 10−2 M of the cited anions.
The results indicated that SO3 2− , S2− , SCN− and S2 O3 2− anions promote the chloride-pitting propagation kinetics. The pitting potential of
304 SS decreases linearly with increasing chloride concentration while it was temperature independent in chloride and chloride containing
sulphur anions in the range from 40 to 70◦ C. Scanning electron microscopy (SEM) observations indicated that open pit with 250 ␮m in
diameter produced on the steel in 0.1 M NaCl under constant potential of +320 mV. While salt film formation inside open pits produced
in the presence of sulphur containing anions with chloride. The pit morphology and its diameter depend on the type of sulphur containing
anion present. ©2000 Elsevier Science S.A. All rights reserved.
Keywords: Stainless steel; Pitting; Chloride; Sulphur species

1. Introduction that the relative concentrations of sulphate and thiosulphate

The failure of some stainless steels resulting from pitting
corrosion is sometimes considered a technological problem
[1]. Consequently, much effort has been expended in at-
tempting to understand and overcome the pitting corrosion.
Therefore, many stainless steels/environment combinations
have been studied [2]. Perhaps the greatest research effort
has been concentrated on the localized corrosion of stain-
less steels in chloride [3–5], bromide [6] chloride/sulphide
[7], bromide/sulphide [8] and chloride/thiosulphate [9] re-
flecting the preeminence of SS as construction material for
many industrial process plants.
The pitting corrosion of AISI 304 SS in paper machines
is particularly surprising since it occurs on nonsensitized
material in water of low chloride content. Thiosulphate is
present in some paper machine white water because of the
use of sodium hydrosulphite as a brightening agent for news
print. Newman et al. [10], reported that chloride ions were
not necessary for thiosulphate pitting of 304 SS provided
∗ Corresponding author.
were in a narrow range. Wang et al. [3], emphasized the es-
sential role of temperature-affected variations of the protec-
tive properties of oxide films formed on the surface of 304
SS in chloride solution.
Newman [11], found that pitting of Fe-19Cr-10 Ni occurs
over a limited range of potentials in sulphate–thiosulphate
solution, the upper limit of potential probably corresponds
to that at which adsorbed sulphur species can no longer be
generated to activate the pitting dissolution. Ke and Alkire
[12] observed that inclusions of MnS and MnS/oxide larger
than 0.7 ␮m initiated stable pitting on 304 SS in dilute salt
solution while other investigators [13] have also found that
mixed sulphide inclusions were the most effective nucleation
sites for pitting. Stewart and Williams [14] observed that
pit nucleation occurred primarily at sulphur-rich inclusions.
They believed that pits would not nucleate if spheroidal in-
clusions were smaller than 0.5 ␮m.
It was, therefore, an objective of this work to study
the influence of the presence of various concentrations of
Na2 S2 O3 , Na2 S, Na2 SO3 , NH4 SCN and Na2 SO4 on the
pitting corrosion behaviour of 304 SS in 0.1 M NaCl.

0254-0584/00/$ – see front matter ©2000 Elsevier Science S.A. All rights reserved.
PII: S 0 2 5 4 - 0 5 8 4 ( 9 9 ) 0 0 2 0 6 - 0
68 E.A. Abd El Meguid et al. / Materials Chemistry and Physics 63 (2000) 67–74
Table 1
The pits charge and size, and the average of pit diameter calculated from current-time curves integration and SEM micrographs, respectively in different
solutions under test
Solution Pitting charge (mC)
0.1 M NaCl 360
0.1 M NaCl + 10−2 M Na2 SO4 300
0.1 M NaCl + 10−2 M Na2 SO3 600
0.1 M NaCl + 10−2 M Na2 S 720
0.1 M NaCl + 10−2 M NH4 SCN 780
0.1 M NaCl + 10−2 M Na2 S2 O3 5880
2. Experimental
The working electrode was made of austenitic 304 stain-
less steel (304 SS) with the following chemical composi-
tion (wt.%) C : 0.08, Mn : 2.0, P : 0.045, S : 0.03, Si : 1.0,
Cr : 18.2, Ni : 8.12, Mo : 0.15, Cu : 0.75 and balance Fe.
The 304 SS rod was machined in the shape of a cylinder
and the experiments were carried out on the top of the cylin-
der in a meniscus position, with an exposed surface area
of 1 cm2 . The electrode was mechanically polished with an
emery paper to a mirror like finish and rinsed with distilled
water. Potentiodynamic anodic polarization technique was
utilized, at the beginning of each experiment, the electrode
was immersed in the test solution for 1 h at the open cir-
cuit potential. The auxiliary electrode was a platinum wire,
while a saturated calomel electrode (SCE) connected to the
cell by a bridge with a Luggin capillary served as the ref-
erence electrode. All potentials quoted in the paper refer to
this electrode.
The induction time (τ ) for pitting corrosion is the time
required for pitting growth under potentiostatic conditions.
The τ value was measured as the time elapsed between po-
tential application (+320 mV/SCE) and the gradual increase
in the current density. The τ depends upon the composition
of the solution under test. The more aggressive the solution
the shorter is the induction time. The electric charges asso-
ciated with the onset of pitting were calculated by integrated
the current-time curves. By considering the dissolution of
1 mm3 of the steel corresponds to 30 C of electricity [15],
the total pits size were calculated and summarized in Table
1. Scanning electron microscopy (SEM) was used to inves-
tigate the surface morphology after induction time experi-
ments.
The solutions were prepared using analytical grade (BDH)
and doubly distilled water. The pH was adjusted by adding
HCl or NaOH. The cell capacity was about 600 ml. The ex-
periments were performed at the desired temperature under
thermostatic conditions.
3. Results and discussion
The effect of chloride concentration on the anodic po-
larization behaviour of 304 SS electrode at scan rate of
Calculate total pit size (mm3 ) The average of measured pit diameter (␮m)
0.012 250
0.01 75
0.02 155−125
0.024 175−115
0.026 300
0.196 350
40 mV/min is shown in Fig. 1a. The chloride concentration
is observed to have only minor effects on the passivation
current of the steel. The most pronounced effect is associ-
ated with the pitting potential (Epit ), at which the anodic
current begins to increase sharply. The Epit value decreases
with increasing chloride ion concentration. According to the
present understanding of the pitting corrosion process the
Epit represent a critical threshold value, where metastable pit
nuclei may be transformed into stable growing pits. In the
case of stainless steels, the stable pit is reached when activat-
ing conditions are established within the pit such as low pH
value and high chloride concentration (salt film formation)
which are necessary to maintain the pits over an extended
time [16]. The Epit values shift in the noble direction with
decreasing chloride concentration (Fig. 1b). At chloride lev-
els below 10−3 stable nucleation of pits is not evident. The
linear dependence of Epit on log [Cl− ] represented by
Epit = A + B log[Cl− ]
Where A and B coefficients are constants, B value is
130 mV/decade which is quite close to values obtained for
higher Mo containing SS such as 316 l [4,17] and 904 l [5]
in aerated chloride solution. Therefore, it would be con-
cluded that B values do not depend on the molybdenum
content in the steel.
The relation between Epit of 304 SS and temperature in
0.1 M NaCl in the presence and absence of 10−2 M of ei-
ther Na2 SO4 , Na2 S2 O3 , Na2 S or NH4 SCN is illustrated in
Fig. 2. It is clear that Epit did not change sensitively with
temperature in the range from 40 to 70◦ C, but it increases
when the temperature decreases to 30◦ C by 350 mV. In the
presence of Na2 S2 O3 , Na2 S or NH4 SCN in the chloride so-
lution, the Epit values drop in the active direction by 200 mV
while in the presence of Na2 SO4 , Epit values shift to more
noble values by 50 mV. This behaviour indicates that the al-
loy would be appreciably more resistant to pitting corrosion
at low temperature and Epit depends on the electrolyte com-
position.
The chloride pitting corrosion of 304 SS is influenced by
the presence of sulphate ions as in Fig. 3. The addition of
sulphate ions to 0.1 M NaCl increases Epit , at and above
1 M Na2 SO4 , the pitting was suppressed. The results reveal
that the competitive adsorption between Cl− and SO4 −2 on
the surface lead to inhibit the pitting attack. However, the
 E.A. Abd El Meguid et al. / Materials Chemistry and Physics 63 (2000) 67–74 69

Fig. 1. (a) Anodic polarization curves for 304 steel in NaCl solutions at different concentrations at 30◦ C. (b) Effect of NaCl concentrations on Epit 304
of steel.

dissolution of 304 SS in the transpassive potential region in

pure sulphate solution could be attributed to the dissolution
of Cr in the steel [18].
The potentiodynamic anodic scans of 304 SS in 0.1 M
NaCl with and without increasing amounts of added
Na2 S2 O3 , Na2 SO3 and NH4 SCN, respectively, are shown
in Figs. 4–6. In pure solutions of 10−2 M of Na2 S2 O3 ,
Na2 SO3 and NH4 SCN, the anodic scans of 304 SS did not
show any sign for pitting initiation, but in pure 0.1 M NaCl
the anodic scan exhibits passivity breakdown at 320 mV.
The addition of these sulphur compounds up to a certain
specific concentration to chloride has significant decreas-
ing effect on Epit However, increasing the concentration of
sulphur species above a critical value causes a significant
increase in Epit These results indicate that the surface of
stainless steel remained passive in sulphur containing solu-
tions and that the chloride was necessary for breakdown of
the passive film. For instance, the increase of thiosulphate Fig. 2. Temperature dependence of Epit of 304 steel in 0.1 M NaCl with
concentration from 10−5 to 10−1 M, moves Epit in the and without different sulphur species.
negative (active) direction than that Epi , recorded in 0.1 M
NaCl only, while at and above 0.2 M thiosulphate concen-
S + 2H+ + 2e− = H2 Saq
tration, Epit increases in the positive direction. This trend
n
could explain in the view of the electrochemical reduction H2 Saq + Mn+ = MSn/2 + nH+
of thiosulphate anions [17]. 2
Where Mn+ were Fe, Ni or Cr ions which were produced
+ −
S2 O3 2−
+ 6H + 4e = 2S + 3H2 O by chloride pitting. Thus, the presence of low concen-
70 E.A. Abd El Meguid et al. / Materials Chemistry and Physics 63 (2000) 67–74

Fig. 3. Anodic polarization curves for 304 steel in 1 M Na2 SO4 and 0.1 M NaCl with and without different concentrations of Na2 SO4 .

Fig. 4. Anodic polarization curves for 304 steel in 10−2 M Na2 S2 O3 and 0.1 M NaCl under the influence of increasing amounts of added Na2 S2 O3 .

tration of thiosulphate in 0.1 M NaCl promotes the pit-
ting corrosion through catalyzes the anodic dissolution
of the steel [19]. Therefore, it could be conclude that
thiosulphate anions, when present at low concentration
(0.1 M) enhance the growth rate of pits. While the inhi-
bition effect of high concentration of thiosulphate anions
(0.2 M) could be due to the preferential electromigration
of S2 O3 2− anions into the pits, preventing chloride and
probably retarding local acidification owing to the reaction
[20].
S2 O3 2− + 6H+ + 4e− = 2S + 3H2 O
The relations between Epit and logarithm sulphur com-
pounds concentration are demonstrated in Fig. 7. The Epit
shifts to more negative (active) values with increasing
the concentration of NH4 SCN, Na2 S2 O3 and Na2 S up to
0.1 M. At higher concentrations (0.1 M) of NH4 SCN and
Na2 S2 O3 , Epit increases with increasing the concentra-
tion, but in the case of Na2 SO3 , Epit shifts to more active
potential and the lower the amount of sulphite addition,
the more active is Epit The stimulating influence of these
anions could be ascribed to their adsorption on the steel
surface and subsequent formation of elemental sulphur or
SH− which accelerate the kinetics of the pitting corrosion
 E.A. Abd El Meguid et al. / Materials Chemistry and Physics 63 (2000) 67–74 71

Fig. 5. Anodic polarization curves for 304 steel in 10−2 M Na2 SO3 and 0.1 M NaCl under the influence of increasing amounts of added Na2 SO3 .

Fig. 6. Anodic polarization curves for 304 steel in 10 M NH4 SCN and 0.1 M NaCl under the influence of increasing amounts of added NH4 SCN.

growth, electromigration of S2 O3 2− or SCN− anions at
high concentrations, into the pits retard the migration of
Cl− ions and decreases the local acidification inside the pit.
While the competitive adsorption between Cl− and SO4 2−
on the surface leads to increased Epit .
Potentiodynamic anodic polarization curves of 304 SS in
10−2 M Na2 S, 0.1 M NaCl and 0.1 M NaCl containing dif-
ferent concentrations of Na2 S are presented in Fig. 8. In
10−2 M Na2 S, the anodic scan exhibits an anodic peak at
−200 mV with no sign for passivity breakdown, while in
0.1 M NaCl with different Na2 S concentrations the pitting
corrosion of steel enhances with increasing the amount of
Na2 S added. This behaviour could be related to the elec-
trodeposition of elemental sulphur on the steel surface [8]
and consequently the repassivation process is inhibited due
to the autocatalytic effect [21] of SH− .
When pitting is initiated, there is an increase in the current
density and the time elapsed between potential application
and current increase is a measure of the induction time. Typ-
ical current density versus time curves for 304 SS in 0.1 M
72 E.A. Abd El Meguid et al. / Materials Chemistry and Physics 63 (2000) 67–74

Fig. 7. The relation between Epit and sulphur compound concentrations.

Fig. 8. Anodic polarization curves for 304 steel in 10−2 M Na2 S and 0.1 M NaCl under the influence of increasing amounts of added Na2 S.

NaCl without and with 10−2 M of Na2 S, Na2 S2 O3 , Na2 SO4 ,
Na2 SO3 or NH4 SCN at constant potential of +320 mV are
illustrated in Fig. 9. It is clear that the addition of 10−2 M
Na2 SO3 to 0.1 M NaCl strongly reduces the τ value than
that recorded in 0.1 M NaCl whereas other sulphur species
have a little effect on the τ value.
The charge consumed during the pitting growth for
10 min in solutions under test and under applied potential
of +320 mV are given in Table 1. It also contains the pit
size calculating from the pitting charge values using the
fact that the dissolution of 1 mm3 of steel (specific gravity
7.89) corresponds to 30 C [15]. It is obvious that the pits
sizes are proportional with the charge value.
The pitting charge magnitude in the presence of sulphur
species increases in the following order SO4 2− < SO3 − <
S2− < SCN− < S2 O3 2− . This reflects the effect of sul-
phur species on the pitting growth kinetic. Therefore,
the adsorption mechanism for pitting corrosion seems
to be more effective in the interpretation of the present
results.
 E.A. Abd El Meguid et al. / Materials Chemistry and Physics 63 (2000) 67–74 73

Fig. 9. Current density versus time for 304 SS in 0.1 M NaCl without and
with 10−2 M of different sulphur containing species at constant potential
of +320 mV.

The occurrence of pitting corrosion on 304 SS in 0.1 M

NaCl without and with sulphur species at constant potential
of +320 mV for 10 min was confirmed by using SEM. The
average of the pit diameter is given in Table 1. The typical
micrographs of the pits obtained are shown in Figs. 10 and
11. It is observed that the pits formed in 0.1 M NaCl are few
in the number and a circular with diameter of 250 ␮m (Fig.
10a). It is reported by Beck et al. [22] that the round pits of
5 ␮m diameter which are formed on 304 SS in the chloride
solution spontaneously repassivated due to the presence of a
resistive surface layer of salt film. However, the appearance
of pit grown in 0.1 M NaCl in this investigation was similar
to that reported recently by Laycock et al. [23]. Therefore, it
was concluded that a solution of 0.1 M NaCl is sufficiently
aggressive under applied potential of +320 mV to sustain
pitting on 304 SS. The presence of 10−2 M Na2 SO4 with
0.1 M NaCl decreased the pit diameter to 75 ␮m (Fig. 10b),
this is an indication on the inhibition effect of SO4 2− ions.
However, the pits obtained in 10−2 M NH4 SCN + 0.1 M
NaCl are 300 ␮m in diameter and contain some corrosion
product inside them (Fig. 10c).
The pits observed in the presence of 10−2 M Na2 S2 O3 Fig. 10. SEM micrographs of the pits obtained on 304 SS after anodic
or 10−2 M Na2 SO3 with 0.1 M NaCl (Fig. 11a and b) were treatment at +320 mV in (a) 0.1 M NaCl, (b) 0.1 M NaCl + 10−2 M
open. Cracked salt film was noticed inside the pits and the Na2 SO4 and (c) 0.1 M NaCl + 10−2 M NH4 SCN.
joining of two or three pits were also observed. On the other
hand, the pits (Fig. 11c) obtained in 10−2 M Na2 S + 0.1 M
NaCl are covered by a porous layer that is a remnant of the
passive film. Destroying such covers during the growth of
the pit may be lead to repassivation of the pit [17].
74 E.A. Abd El Meguid et al. / Materials Chemistry and Physics 63 (2000) 67–74
Fig. 11. SEM micrographs of the pits obtained on 304 SS after anodic
treatment at +320 mV in (a) 0.1 M NaCl + 10−2 M Na2 S2 O3 (b) 0.1 M
NaCl + 10−2 M Na2 SO3 and (c) 0.1 M NaCl + 10−2 M Na2 S.
4. Conclusions
Electrochemical potentiodynamic anodic polarizations
have shown that SO4 2− , SO3 2− , S2− , SCN− or S2 O3 2− an-
ions alone did not produce pitting initiation on 304 SS but
the presence of low concentration of SO3 2− , S2− , SCN−
or S2 O3 2− anions significantly promote the chloride pitting
propagation kinetics. The addition of sulphate anions to
chloride ions retards the pitting propagation. It was found
that the thiosulphate anions are the most aggressive sulphur
containing anions. The aggressive action of the presence of
sulphur containing species with chloride ions is confirmed
by induction time measurements at constant potential of
+320 mV as well as SEM observations. The results were
interpreted in view of the adsorption theory. The critical
chloride concentration to produce pitting corrosion of 304
SS was 10−3 M. The Epit values decreased with increasing
chloride ion concentration but it did not affected in the
change of temperature from 40 to 70◦ C. SEM observations
showed that circular open pits were obtained on 304 SS
after potentiostatic anodic treatment at +320 mV in 0.1 M
NaCl while in the presence of sulphur anions with chloride,
salt film precipitated inside the open pits were obtained.
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