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Limiting conditions for pitting corrosion of stainless steel EN 1.4404 (316L) in

terms of temperature, potential and chloride concentration

Article  in  Materials and Corrosion · January 2013

DOI: 10.1002/maco.201609061

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272 DOI: 10.1002/maco.201609061 Materials and Corrosion 2017, 68, No. 3

Limiting conditions for pitting corrosion of stainless steel

EN 1.4404 (316L) in terms of temperature, potential and
chloride concentration
S. H. Mameng*, R. Pettersson and J. Y. Jonson

The main stainless steel grades used for water applications are 1.4307 and
1.4404. The grade selection depends on the conditions: 1.4404 is a more
conservative choice and has an improved corrosion resistance over 1.4307. This
paper addresses the concept of defining limiting conditions for pitting corrosion
of 1.4404 in terms of the environmental parameters such as temperature,
potential and chloride concentration. Extensive testing has been done with a
combination of short-term electrochemical measurements and long-term
chlorination experiments. Results are discussed in the light of the current
understanding of the critical levels of key parameters for pitting corrosion.

1 Introduction been done with a combination of short-term electrochemical

The austenitic stainless steel EN 1.4404 (316L) is considered to be
one of the more resistant of the basic standard stainless steels to
chloride environments and is therefore an important steel grade
for water applications such as potable water piping and cooling
water systems. The corrosion resistance of this stainless steel
grade is provided by the chromium content in combination with
molybdenum. An oxide layer is formed on the surface of material
and this passive layer protects the steel against the aggressive
environment [1]. However, like other stainless steels, this grade
may suffer localised corrosion in chloride-containing environ-
ments, limiting its use in different applications.
The pitting corrosion behaviour of stainless steel in chloride
environment has been extensively investigated as a function of
environmental variables [2–16]. The chloride concentration and
temperature are the most important parameters that affect the
pitting resistance of stainless steel and both decrease the pitting
potential [2–5]. Besides the influence of pH and dissolved oxygen,
the effect of anions such as perchlorate ion, thiosulfate ion, etc.
has also been investigated [2–4,8,9]. A very extensive analysis of
published data is available in Ref. [7]. This paper addresses the
concept of defining limiting conditions for pitting corrosion of
EN 1.4404 in terms of the environmental parameters tempera-
ture, potential and chloride concentration. Extensive testing has
S. H. Mameng, J. Y. Jonson
Avesta Research Centre, Outokumpu Stainless steel AB, Koppar-
dalsva€gen 65, P.O. Box 74, SE-774 22 Avesta (Sweden)
E-mail: sukanya.mameng@outokumpu.com
R. Pettersson
€dg-
Jernkontoret – The Swedish Steel Producers’ Association, Kungstra
årdsgatan 10, P.O. Box 1721, 111 87 Stockholm (Sweden)
measurements and long-term chlorination experiments.
2 Experimental
2.1 Material
The material used in this study was the standard austenitic
stainless steel EN 1.4404, tested as sheet and welded specimens.
All specimens have the same thickness of 3 mm. The actual
chemical composition of EN 1.4404 is given in Table 1.
2.2 Pitting corrosion testing
Two test programmes were used for this investigation: a short-
term electrochemical test, which was supplemented by potentio-
static exposures in critical cases, and a long-term immersion test.
Both aim to determine limiting conditions for pitting corrosion
of EN 1.4404 in terms of temperature, potential and chloride
concentration.
2.2.1 Potentiodynamic polarization measurements
Pitting potential measurements (Epit) were performed in
chloride solution at different temperatures. Specimens of size
30
30
3 mm were used and were wet ground to 320 grit at
least 18 h before testing, then immediately before the experiment
cleaned with ethanol. Polarization curves for the different steels
were obtained in solutions with chloride ion concentrations
between 35 and 100 000 ppm (mg/L) at different temperatures
from 10  1 to 80  1 8C. In order to eliminate the influence of
crevice corrosion, the Avesta cell (Fig. 1) [6] was used in all the
electrochemical experiments where the chloride content was
1000 ppm or higher. For chloride concentrations of 355 ppm or

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Materials and Corrosion 2017, 68, No. 3
Table 1. The actual chemical composition for EN 1.4404
Typical composition (wt%)
C Cr Ni Mo N Si Mn
0.021 17.2 10.1 2.1 0.038 0.45 1.65
lower, a hydrophobic washer (silicone-based dental putty; provo
Novil Putty-Soft fast set, Heraeus) with teflon spray (Cargo-Oil)
was used to cover the crevice area of the specimen.
Polarisation measurements were made using a Solartron
1287 potentiostat. The potential of the working electrode was
measured versus a saturated calomel (SCE) reference electrode.
The auxiliary electrode was platinum (Pt) wire. Dissolved oxygen
was maintained at a low level by bubbling nitrogen through the
sodium chloride solution during the whole test time. Before each
polarization measurement, the open circuit potential (OCP) was
measured for 10 min in the test solution. The polarisation started
at 300 mV (SCE) and the scan rate was 20 mV/min. Epit was
defined at the point where the current exceeds 100 µA/cm2
[17] and remains above this level for at least 1 min as shown in
Figure 1. Avesta electrochemical cell used to avoid crevice corrosion
www.matcorr.com
Limiting conditions for pitting corrosion of stainless steel 273
Fig. 2. Duplicate samples were tested and gave in most cases
a difference of <100 mV (SCE). If larger differences were
observed, additional measurements were made.
Cu
0.39 2.2.2 Potentiostatic measurements
For cases in which the potentiodynamic results gave question-
able results, potentiostatic experiments were also carried out. A
specimen was held at a given temperature in the solution at an
applied constant potential close to Epit evaluated from the anodic
polarisation curve. These experiments were carried out in
1000 ppm chloride solution at 30–60 8C and potentials of 400,
500 and 600 mV (SCE). Before each measurement, the open
circuit potential (OCP) was measured for 10 min, then the
potential was increased at 20 mV/min from the starting potential
of 300 mV (SCE) up to the set potential for the potentiostatic
experiment. The current was then monitored for a test period of
3 h. The solution was purged with nitrogen throughout the test.
2.3 Long-term chlorination test of welded samples
Welded samples were tested by long-term immersion in a slightly
chlorinated environment at different temperatures. The welded
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
274 Mameng, Pettersson and Jonson Materials and Corrosion 2017, 68, No. 3

chloride concentrations and temperatures. Typical curves for

Figure 2. Typical polarisation curves obtained in sodium chloride
solution (Curve A: higher chloride and temperature, Curve B: low
chloride and temperature, Curve C: transpassive behaviour with a
breakdown potential above 1.200 V (SCE))
samples were produced by tungsten inert gas welding (TIG),
using a filler material and welding conditions as specified in
Table 2. Coupons of duplicate welded specimens with size
60
30
3 mm were used and all cut edges were wet ground to
320 grit. In order to remove weld oxides, samples were pickled
in mixed acid (3 M HNO3 and 3 M HF) for 3 min at 53 8C.
The test solutions were prepared from distilled water and
sodium chloride to give chloride ion levels in the range of 100–
100 000 ppm. The pH was in all cases in the range 6.5–7.5. The
solutions were dosed with sodium hypochlorite (1000 ppm) to
give 1 ppm residual chlorine concentrations. The residual
chlorine level was measured with colorimeter using the
diethyl-p-phenylene diamine (DPD) method. The redox potential
was typically in the range 650–750 mV (SCE) [8]. Immersion tests
were carried out for 30 days at various temperatures (20–80 8C).
The depth of maximum attack was measured with a light optical
microscope and a depth of attack of at least 0.025 mm was
defined as the pitting corrosion. The open circuit potential was
monitored in some cases.
evaluation of Epit are illustrated in Fig 2. At lower chloride levels
and temperatures, the Epit was high and the current increased
slowly with increasing potential (Curve B) when pitting occurred.
At higher chloride levels and temperatures, pitting propagated
more rapidly, so the current increased much faster and at a
lower potential (Curve A). In the absence of pitting, a very gradual
current increase at transpassive potentials was seen (Curve C).
In all cases specimens were evaluated in a stereo microscope
after testing, to verify that pitting corrosion was present.
The pitting potential was defined as the potential where the
current continuously exceeds 100 µA/cm2. The reason for using
this current density and not 10 µA/cm2 is that the metastable
pitting could give current peaks above 10 µA/cm2 so clear
identification of stable pitting required the higher threshold.
This approach also avoided any uncertainty in cases when the
passive current density was relatively high value. The pitting
potentials evaluated at 10 and 100 µA/cm2 are shown in Fig. 3,
which demonstrates that there is little difference at lower
potentials but some deviation at higher potentials.
Figure 4 shows the relationship between Epit and chloride
concentration at different temperatures and indicates that the
Epit decreases as the logarithm of the chloride concentration
increases. At the lowest chloride level investigated (35 ppm)
transpassive behaviour with a breakdown potential above
1200 mV (SCE) is seen at temperatures up to 50 8C (Curve C
in Fig. 2). As the chloride level is increased to 100 ppm there is a
fairly sharp drop in the critical potential and pitting occurs at
approximately 700 mV (SCE) at temperatures of >20 8C (Fig. 4a).
This sharp drop extends up to 355 ppm at temperatures of
>50 8C (Fig. 4b). Thereafter the decrease in pitting potential is
more gradual.
Figure 5 shows the same data plotted as a function of
temperature. This relationship has frequently been used to
define a critical pitting temperature [2–6,10,14,15], particularly in
cases in which there is a sharp transition. The results indicate
that the pitting potential Epit was only weakly dependent on the
temperature in the bulk solution, particularly at chloride
concentration higher than 3545 ppm, see Fig. 5b. This indicates

3 Results

3.1 Influence of chloride concentration and

temperature on pitting potential

Potentiodynamic anodic polarization curves were used to

determine the pitting potential (Epit) for EN 1.4404 at different

Table 2. Welding condition of welded specimens

Base Welding Shielding Welding Heat Joint

material wire TIG gas speed input design
(EN ISO (cm/min) (kJ/cm)
14343)

EN W 19 12 Argon gas 24.66 0.60 Butt

1.4404 3 L Si (Ar) joint Figure 3. Epit of EN 1.4404 was determined at a critical current limit of
10 and 100 µA/cm2

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Materials and Corrosion 2017, 68, No. 3
Figure 4. Effect of chloride concentration on Epit of EN 1.4404 at different temperatures
that the protective efficiency of the passive film is relatively
insensitive to temperature.
3.2 Construction of engineering diagrams for pitting
corrosion
The pitting potential results were used as a basis for constructing
engineering diagrams showing the risk areas for pitting in terms
of chloride concentration and temperature. The idea of engineer-
ing diagrams based on Epit measurements has been presented
earlier, for example by Fielder and Johns in 1989 [3]. In the present
study, the diagrams are obtained by mapping the regions in which
pitting occurs at different given potentials as shown in Fig. 6. The
critical potential used for defining the boundary was set at various
levels in the range 300–700 mV (SCE). The solid points indicated
that Epit is lower than the selected potential and open points
indicate that it is higher or equal. When used in combination with
knowledge of the corrosion potential in a system containing
various oxidising species [2–8] such diagrams can be used to
assess the corrosion risk.
The diagrams for EN 1.4404 at all the five selected potentials
are plotted together in Fig. 6f. The curves are largely parallel,
and have a S-shaped form, with a chloride sensitive (largely
Figure 5. Effect of temperature on Epit of EN 1.4404 at different chloride concentrations
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Limiting conditions for pitting corrosion of stainless steel 275
temperature insensitive) regime at low chloride levels, an
intermediate regime in which the potentials are strongly
influenced by temperature (but largely insensitive to chloride
concentration) and a chloride-sensitive/temperature-insensitive
regime at the highest chloride levels. The only exception of
the general shape is seen at 500 mV (SCE), where there is a more
linear trend which was confirmed by repeated measurements.
The effect of the choice of current density criterion of 100
or 10 µA/cm2 for evaluation of the pitting potential is illustrated
for Fig. 7. This shows that for the lower potential of 400 mV
there is no difference between the two criteria, while at 700 mV
a more conservative line results from the use of the lower
10 µA/cm2 criterion.
3.3 Potentiostatic determination of pitting potentials
In this part of the investigation, a constant potential, Eapp in the
range 400–600 mV (SCE) was applied. The intention was to
obtain more information about the pitting behaviour at 500 mV
(SCE), where there was a deviant linear trend in the engineering
diagram, Fig. 6f. The current density was monitored as a function
of time at the imposed potential and examples of the results are
shown in Fig. 8.
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
276 Mameng, Pettersson and Jonson
Figure 6. Potential diagram for EN 1.4404 at the different selected potentials
Figure 8a shows the current evolution at 400 mV (SCE) at
three different temperatures, all of which were below the critical
temperature for pitting determined from the potentiodynamic
experiments. In all cases, the current density decreased gradually
with time and no pitting was observed. Figure 8c shows
corresponding data for an applied potential of 600 mV (SCE) at
three temperatures. 30 8C is below the potentiodynamically
determined critical pitting temperature and shows only low
current densities, note that the vertical scale is much larger here
than for Fig. 8a so this curve appears flat. At 40 and 50 8C, the
current density increased rapidly to high values and pitting
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Materials and Corrosion 2017, 68, No. 3
corrosion was observed. The conclusion is that at both 400 mV
(SCE) and 600 mV (SCE) there is good correspondence between
the potentiodynamic and potentiostatic results. However, at
500 mV (SCE) significant differences are observed. All three
temperatures investigated in Fig. 8b were below the potentiody-
namic critical temperature but in all cases there was an increase
in current density after a short incubation time, and pitting
was observed on the specimens after testing. A compilation
of data at the three imposed potentials is given in Fig. 8d,
clearly illustrating that there is a difference in behaviour
between potentiostatic and potentiodynamic testing at 500 mV
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Materials and Corrosion 2017, 68, No. 3
Figure 7. Potential diagram at 400 and 700 mV (SCE) for EN 1.4404
showing a shift in the limiting line for pitting when different current
density criteria are used to evaluate the pitting potential at 700 mV but
not at 400 mV
(SCE). It appears that the existence of an incubation time
means that the rate of potential increase dE/dt shifts the pitting
potential to higher values compared to potentiostatic testing.
If the potentiostatic data at 500 mV (SCE) is included in the
Figure 8. Current density versus time curves in 1000 ppm chloride solution at different temperatures and applied potentials
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Limiting conditions for pitting corrosion of stainless steel 277
engineering diagram at this potential, Fig. 9, it is seen that there
is the same type of S-shaped curve as at other temperatures.
3.4 Immersion tests in chlorinated solutions
To assess the relevance of the engineering diagrams to longer-
term service performance, laboratory immersion tests were
performed to simulate the same corrosive environments. In
these tests, an elevated potential is achieved using sodium
hypochlorite addition to give 1 ppm residual chlorine in chloride
environments at 20–80 8C. The residual chlorine acts as an
oxidant and increases the risk of localised corrosion [8]. The
tested samples were examined after exposure in the chloride
environments for 30 days. A summary of the results is shown in
Table 3. The open circuit potential (OCP) was observed to be in
the range 600–800 mV (SCE) as shown in Fig. 10. There was a
slight decrease in the OCP with increased temperature; this
is because a higher temperature decreases the equilibrium
potential.
The results from the long-term chlorination tests can be
used to construct the same type of concentration-temperature
maps as for the short-term tests. The data are shown in Fig. 11
and represent the maximum temperatures and chloride
concentrations which can be tolerated in slightly chlorinated
(1 mg/L) chloride environments.
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
278 Mameng, Pettersson and Jonson Materials and Corrosion 2017, 68, No. 3

Epit ¼ 3:165  1:943 log ½Cl   0; 0009 ½T

þ0:572 log ½Cl 2 þ 0:00015 ½T2


0:007 ½T log½Cl   0:056 log Cl 3

þ0; 00000169 ½T3 þ 0; 00038 T log Cl 2

þ0; 0000418 ½T2 log½Cl  ð1Þ

Figure 9. Potential diagram for EN 1.4404 at 500 mV (SCE) selected
potential
4 Discussion
4.1 Modelling the influence of chloride and
temperature on the pitting potential
Pitting corrosion is one of the most critical types of localised
corrosion, since it can lead to failure of structural components
and affect their service life. Figures 4 and 5 clearly show that the
Epit decreases with increasing temperature at different chloride
concentrations. These results are in agreement with other
researchers [9–16,18–24].
The potentiodynamically determined pitting potentials were
used as a basis for developing descriptive equations to predict the
pitting performance of EN 1.4404 stainless steel. The multivari-
ate data analysis program Simca (Umetrics) was used to assess
the significance of different possible factors and combinations of
factors on the pitting potential, Fig. 12.
Based on this, two different linear regression models were
used to describe the experimental data. The first, full model
used all the factors in Fig. 12 and yielded the relation
(Equation (1)):
where the Epit is called the pitting potential (V vs. SCE), [Cl] is
the chloride ion concentration (ppm) and T is the temperature
( 8C). This gave an excellent fit to the experimental data,
with a coefficient of determination, R2 ¼ 0.958 as shown in
Fig. 13. This suggest that the pitting model can efficiently
simulate the intricate inter-relationship between the Epit and
various environment parameters, and predict the critical
pitting potential of EN 1.4404 as a function of chloride ion
concentration and temperature. This could potentially be
useful in connection with service monitoring to warn of the
danger of pitting when environmental parameters change over
time. However, this complicated model is difficult to connect
to physical reality.
A simplified model was therefore developed using linear
regression with the first three factors from Fig. 12. This yielded
Equation (2) and still gave a reasonable fit to the experimental
data, with a coefficient of determination, R2 ¼ 0.889 as seen in
Fig. 14.
Epit ¼ 1:945  0:493 log ½Cl   0:0057 ½T þ 0:0430 log ½Cl 2
ð2Þ
The inflection seen in the curves at very high chloride
concentrations (to give the second chloride-insensitive regime)
could perhaps be regarded as a very special case. However,
removal of these values has only a small effect on the coefficient
of determination, increasing it to R2 ¼ 0.896.
Even in the simplified case, the role of the chloride ion
seems complicated, with both a negative coefficient for chloride
(i.e. chloride decreases the pitting potential) and a positive

Table 3. Summary of visible pitting corrosion in this investigation

Appearance of pitting attack after 30 days

Chloride concentration (ppm) 20 8C 30 8C 40 8C 50 8C 60 8C 80 8C

100 – – o – o o
200 – o – o – o
300 – – o – o o
500 o o o x, w, e – –
1000 o – o – – –
5000 o – – – – –
10 000 o x, w, e x, w, e – – –
35 450 x, w, e x, w, e – – – –
100 000 x, w, e – – – – –

o, No corrosion; x, pit attack on base material; w, pit attack on weld area; e, edge attack; (–), not tested in this study.

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Materials and Corrosion 2017, 68, No. 3
Figure 10. Open circuit potentials measured in the chlorinated
environments, EOCP(max) (SCE)
coefficient for (Cl)2. In the full model there is an additional
feature of a negative coefficient for (Cl)3, which is necessary in
order to introduce the double inflection seen in the engineering
diagram.
4.2 Three regimes of environmental dependence
An alternative approach to the analysis of the results is to divide the
curves in the engineering diagrams (Fig. 6) into sections. The
S-shape indicates that there are three different regimes: a chloride-
sensitive (or temperature-insensitive) region at high temperature
and low chloride then an intermediate temperature-sensitive (or
chloride-insensitive) regime and finally a second chloride sensitive
(temperature-insensitive) region at high chloride concentrations
and low temperatures, as illustrated in Fig. 15. The central regime
could be regarded as a ‘chloride independent’ critical temperature
Tcrit in the same way as the ‘potential independent’ CPTconcept in
ASTM G150 while the first regions could be regarded as
characterized by a ‘temperature independent’ critical chloride
content, Clcrit. The third region, the ‘brine regime’ at very high
Figure 11. Engineering diagram for EN 1.4404 based on immersion
testing in chlorinated environments
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Limiting conditions for pitting corrosion of stainless steel 279
Figure 12. Multivariate analysis using Simca of factors affecting the
potentidynamic pitting potential
chloride contents, might be regarded as a rather special case in
which the concentration of the solution approaches saturated and
could be expected to promote the formation and maintenance of a
salt film.
An increase in temperature is to be expected to have several
effects. Firstly, the rate of chemical reactions, including metal
dissolution, increases, as does the rate of pit growth as
exemplified by curves A and B in Fig. 2. The characteristics of
the passive film may also change. The high temperature passive
film probably has a different structural characteristic from that
developed at low temperature, due to the thermodynamics of
hydrolysis reaction between the ions of alloying elements such as
iron chromium, nickel, and molybdenum and water molecules at
elevated temperature [25]. The porosity of the passive film has
also been reported to increase with temperature [26] and the
defect structure of the semiconductor anodic film on Fe–Cr–Ni
alloys may change from p-type to n-type with temperature. It has
been argued that n-type films could be more susceptible to pit
initiation than p-type films due to the existence of oxygen
vacancies, which can enhance the transport of chloride ions
through the oxide lattice [27,28]. Additional effects of tempera-
ture include faster diffusion of various species through the oxide
film as well as into and out of the pit [5]. On the other hand, an
increase in chloride content will increase the probability of
adsorption and/or penetration of chloride into the passive
film [5], causing pit initiation. A greater availability of chloride
ions will more readily replace water molecules or hydroxide ions
at undeveloped parts of the passive film (e.g., at H2O-M-OH2
bridges) [25]. It will also favour the transition from metastable to
stable pits by facilitating the formation of a salt film at the pit
mouth [29,30].
A proposed explanation for the shape of the engineering
diagram curve, shown in Fig. 15, is that at sufficiently low
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
280 Mameng, Pettersson and Jonson Materials and Corrosion 2017, 68, No. 3

Figure 13. Application of the full model to the potentiodynamic pitting potential data

chloride contents the initiation process is impeded by the lower pit growth is so slow that it becomes a rate determining
availability of chloride ions. Once Clcrit is exceeded, this ceases process, since the pit chemistry cannot be maintained and pits
to become the rate determining process or at least becomes less passivate. A contributory factor may be a greater rupture
sensitive. On the other hand at sufficiently low temperatures, resistance of the low temperature passive film. Above Tcrit this

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Materials and Corrosion 2017, 68, No. 3 Limiting conditions for pitting corrosion of stainless steel 281

Figure 14. Application of the simplified model to the potentiodynamic pitting potential data

ceases to be a rate-determining process. In intermediate encounted at high chloride concentrations, in the brine regime
conditions, marked by the circle in the figure, there is a marked by a square. In these conditions, the closeness to
unfavourable combination of initiation and propagation which saturation could mean that pit chemistry can be maintained in
leads to pitting. The other set of unfavourable conditions are spite of a low dissolution rate, because the closeness to the

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282 Mameng, Pettersson and Jonson Materials and Corrosion 2017, 68, No. 3

Figure 15. Schematic illustration of the potential diagrams

Figure 16. Comparison between short-term electrochemical test and

saturation point means that a salt film can readily be
maintained.
At 500 mV (SCE) there was a different type of behaviour,
with a straight engineering diagram line rather than an inflection
point. However, this shape was to a large extent discounted as a
result of the potentiostatic experiments, which showed that
pitting could indeed occur in the ‘worst case’ regime if a
sufficient incubation time was allowed. One possible contribu-
tory factor here is that bound water associated largely with
chromium (Cr) has been shown to be strongly influenced by the
applied potential, temperature and time at potential [9,19]. It was
established that the water content in the passive film formed on
Type 304 in deaerated 0.5 M H2SO4 changed abruptly at the
critical potential of 400 mV (SCE) [19]. Epit values determined
from the potentiodynamic method are strongly dependent on
the potential scan rate [20] and it is possible that the overshoot
effect is therefore particularly marked at around such critical
potentials.
4.3 Comparison to long-term chlorination experiments
long-term chlorination test
magnitude in concentration. This underlies the need to
control excursions in potential in water treatment and transport
systems – for example by not overdosing chlorination or addition
of other oxidants.
4.3 Comparison to electrochemical critical pitting
temperature measurements
The concept of raising the temperature at the constant potential in
order to determine the critical pitting corrosion is well established
and included in the standard test methods ASTM G150 and
ISO17864 [17]. The same EN 1.4404 material as in the present
investigation was investigated using this method in Ref. [13], with
the difference that measurements were made at several different
potentials rather than only at the 700 mV (SCE) level described in
the standards. Some typical data are shown together with Epit
data from this study in Fig. 17. Comparing the two types of
measurement methods, it is seen that the general agreement is

Comparison of diagrams between short-term Epit measurement

and long-term curves for EN 1.4404 are shown in Fig. 16. The
short-term curves for both 600 and 700 mV (SCE) were
considered because these correspond most closely to the OCP
in the long-term tests. The comparison shows a good agreement
with behaviour predicted from the Epit data at 100 µA/cm2 and
700 mV (SCE), although the short-term curve is slightly more
conservative. This confirms that the choice of the higher current
criterion from the pitting potential measurements is appropriate.
The reasons for the difference between short-term and long-term
tests may be related to the fact that specimens in the long-term
tests are subject to a gradual potential increase at the start of
the experiment. This may well serve to strength on the passive
film compared to the situation in the short-term tests. Another
difference is that long-term exposures were done on pickled
samples with exposed edges, while the short-term specimens
were ground to 320 grit.
It is clear from these diagrams that the evolved or applied
potential has a major impact on the risk for pitting, shifting the Figure 17. Comparisons of potential effect between Epit data from this
curves several tens of degrees in temperature or orders of investigation and CPT data at different potential [13]

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Materials and Corrosion 2017, 68, No. 3
good, although there can be more than 10 8C difference between
the results of potentiostatic and potentiodynamic measurement.
There are some critical differences between the two types of
measurement methods. In the case of potentiostatic measure-
ments, an applied anodic potential in the passivity domain of
stainless steel enhances the passivity on the entire surface and this
passivity is further modified during the time spent at temper-
atures below the CPTof stainless steel. Hence, the trend is that the
breakdown of a thicker or more stable passive layer occurs at
higher temperatures. It is also important to note that there is a
difference in scatter between the two types of measurements. The
CPT data from the potentiostatic method [13] show a small scatter
under standard conditions, but a larger scatter particularly at lower
concentrations, whereas Epit data in this study give sufficiently
small standard deviations (<100 mV).
The advantage of the potentiostatic CPT method is that it
gives results in a short time period, but the potentiodynamically
based engineering diagrams have a greater accuracy for
evaluation over a broad range of potentials, concentrations and
temperatures. This type of diagram is very useful for material
selection if the potential of the system is known, and can also
serve as a basis for assessment of corrosion risks in service,
particularly if the effect of additional environmental components
can be taken into consideration in the future.
5 Conclusions
1. The chloride concentration and temperature are the most
important environmental conditions that affect pitting resis-
tance of EN 1.4404 and both decrease the pitting resistance.
2. The potentiodynamic polarisation method for determining
pitting potentials is a useful tool and gives sufficiently small
standard deviations to enable definition of engineering
diagrams showing the boundaries between pitting and no
pitting in terms of chloride concentration and temperature.
3. There is generally good agreement between the boundaries
from pitting potential measurements and published data
from potentiostatic critical pitting temperature (CPT) testing,
also between pitting potentials and 1 month exposure testing
in mildly chlorinated chloride solutions.
4. The pitting risk diagram is a useful tool to aid materials
selection, although it is important to realise that additional
factors such as surface condition, flow rate, deposits and the
presence of other environmental species will affect the exact
position of the boundaries.
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(Received: May 9, 2016) W9061
(Accepted: June 10, 2016)
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