Desalination 207 (2007) 268275

Effects of sigma phase precipitation on seawater pitting of

duplex stainless steel
Hosni M. Ezubera*, A. El-Houdb, F. El-Shaweshb
a
College of Engineering, University of Bahrain, PO Box 32038, Bahrain
Tel. +973 (17) 866894; Fax: +973 (17) 680935; email: hzubeir@eng.uob.bh
b
Petroleum Research Center, Tripoli, Libya

Received 21 March 2006; Accepted 26 May 2006

Abstract
In this study the potentiodynamic polarization technique was employed to study the pitting corrosion
characteristics of duplex stainless steel types SAF 2205 and 3RE60 duplex stainless steels in artificial seawater at
various test temperatures (25, 50 and 80EC) and sigma phase precipitation (produced at pre-quenched heat treatment
temperature of 845oC for different heating duration of 10, 60 and 300 minutes). The results showed that mill-annealed
and sigma phase precipitated samples of type 2205 DSS were immune to pitting corrosion at ambient temperature,
however, the alloy exhibited susceptibility to pitting attack at 50EC. The potential necessary to cause pitting corrosion
decreased (became less noble) with increasing test temperature (to 80EC) and/or inappropriate heat treatment duration
and become more effectual with long heat treatment exposure. In contrast, the mill-annealed 3RE60 exhibited
seawater pitting attack at ambient temperature and the intensity of the pitting attack increased with increasing test
temperature or sigma phase precipitation volume. The results clearly indicated that the presence of nitrogen and
relatively higher chromium content in the 2205 alloy is an advantage for seawater pitting corrosion resistance.

Keywords: Duplex stainless steel; Seawater; Pitting corrosion; Sigma phase

1. Introduction steels [14]. DSSs received the name from the

Duplex stainless steels (DSS) are finding
increased application in aggressive marine envi-
ronments because of their superior performance
in comparison to traditional austenitic stainless
*Corresponding author.
fact that their microstructure consists of a bal-
anced mixture of ferrite and austenite phases after
water quenching heat treatment [5]. The ferrite/
austenite phase balance in duplex stainless steel
is achieved primarily by adjusting chromium,
nickel, and nitrogen contents, and by control of
thermal history [6]. The presence of considerable

0011-9164/07/$ See front matter 2007 Published by Elsevier B.V.

doi:10.1016/j.desal.2006.05.021
 H.M. Ezuber et al. / Desalination 207 (2007) 268275
amounts of chromium, molybdenum and nitrogen
gives the duplex alloys outstanding resistance to
pitting attack in chloride containing solutions and
the relatively low nickel content grants them
improvement to stress corrosion cracking in
comparison to conventional austenitic stainless
steels [711]. During exposures in the tempera-
ture range from 320 to 950EC, DSS alloys are
susceptible to the formation of intermetallic
compounds including carbides, nitrides and sigma
phases[12-15]. Sigma () phase consists mainly
of chromium-molybdenum precipitations at the
grain boundary. The precipitation of this phase
induces adverse changes in mechanical properties
and even a few volume fraction percentage points
of -phase can significantly decrease the ductility
and toughness of the material. Sigma is also
detrimental to crevice and pitting corrosion resis-
tance of the DSS alloys and this negative influ-
ence is attributed to the depletion of chromium
and molybdenum at the grain boundaries [1619].
In this study the pitting corrosion behavior of
two different medium duplex stainless steel
grades namely SAF 2205 and 3RE60 was
evaluated in artificial seawater. Although the
nitrogen alloyed DSS (2205) has become a very
successful alternative to the 3RE60 alloy, the
latter still has some applications as seamless
tubing, heat exchangers, and suction roll shells in
paper mills. The SAF 2205 alloy is the most
widely used of the newer duplex alloys and is the
most often found in the form of welded pipes or
tubular components. This alloy is used widely in
environments where resistance to general corro-
sion or localized type attack is important. The aim
of this work is to briefly study the effect of sigma
phase precipitation resulting from improper heat
treatment on the pitting corrosion behavior of
SAF 2205 and 3RE60 alloys in seawater environ-
ments. Also to assess the role of chromium,
molybdenum and nitrogen content on the pitting
corrosion resistance of these alloys as a function
of seawater temperature and sigma phase
precipitation volume.
269
2. Experimental
Pitting corrosion experiments were conducted
using two duplex stainless steel alloy grades, SAF
2205 and 3RE60, in artificial seawater. The
alloys used in this study are of traditional
composition as shown in Table 1. The DSS alloys
studied was in the form of square flat-plate
specimens 3 mm thick with a 5-cm2 surface area
exposed to the test solution. The test samples
were mounted in epoxy resin with an insulated
electrical connection. Specimens were wet-
abraded using progressive grits of silicon carbides
(SiC) up to 1000 grit, rinsed with distilled water,
and immersed immediately into the seawater
solution.
The formation of phase on these specimens
was achieved by heating the samples in a labora-
tory furnace at 845EC for a variety of times (10 or
60 or 300 minutes), followed by water-quench-
ing. Microstructure examination of heat-treated
specimens (in 10 M KOH [20]) are shown in
Fig 1.
The basic test solution used in this work was
artificial seawater. This water was prepared with
the following composition (per liter); sodium
chloride: 25.54 g, magnesium chloride 11.1 g,
sodium sulfate: 4.09 g and calcium chloride:
1.16 g [21].
The electrochemical cell employed in this
study was made of glass beaker suspended in a
water bath with the three electrodes (reference,
counter and test electrodes) immersed directly
into the test solution. A saturated calomel elec-
trode was used normally as the reference elec-
trode, and all potentials were referred to this
scale. A platinum counter electrode also used, and
the potential was swept in the anodic direction
starting from !400 mV at a rate of 1 mV/s until
an anodic current of 100 A/cm2 was exceeded.
The pitting potential (Ep) was defined at the
potential where the anodic current density exhi-
bited a sharp and sustained increase from the
background passive current density.
270 H.M. Ezuber et al. / Desalination 207 (2007) 268275

Table 1
Chemical composition of DSS alloys used in this work

Alloy C Mn P S Si Cr Ni N Mo

SAF 2205 0.03 1.5 0.25 0.28 0.5 22 5.5 0.18 3.2
3RE60 0.02 1.47 0.021 0.026 1.64 18.42 4.84 0.071 2.7

Fe: bal.

Fig. 1. Microstructure of HT (10 min) duplex stainless steel alloys etched in 10 M KOH. (a100). Left: SAF 2205. Right:
3RE60.

3. Results and discussion the pitting potential is negatively shifted from

The effect of seawater temperature and sigma
formation on the pitting behavior of SAF 2205
and 3RE60 duplex stainless steel alloys are
shown in Figs. 2 and 3. At room temperature,
these figures show that mill annealed specimen of
alloy 3RE60 exhibited susceptibility to pitting
attack at 390 mV (SCE). The figures also show
that the pitting potential of this alloy is decreased
with the application of the inappropriate heat-
treatment and attained more negative values with
increasing the duration of inappropriate heat-
treatment, indicating the decrease in pitting
corrosion resistance. With the 10 min HT sample,
390 to 350 mV (SCE). The 60 min and 300 min
HT specimens suffer pitting at 180 and 75 mV
(SCE) respectively, indicating respective negative
shift 210 of and 315 mV. The decrease in pitting
resistance as a result of inappropriate heat-
treatment is related to sigma phase deposition
caused by the inappropriate heat-treatment. The
detrimental effect of sigma on pitting resistance
can be explained by chromium and molybdenum
depletion in the zones next to the growing sigma
phase. These localized areas with lower con-
centrations of the elements Cr and Mo become
susceptible to pitting attack. The rapid deterio-
 H.M. Ezuber et al. / Desalination 207 (2007) 268275 271

Fig. 2. Potential-current density behavior of as received and heat-treated (HT) alloys 3RE60 and SAF 2205 DSS in artificial
seawater at various test temperatures and heat-treatment duration. 1, 2205 MA RT; 2, 2205 HT 300 min RT; 3, 3RE60 MA
RT; 4, 2205 MA 50EC; 5, 3RE60 HT 10 min RT; 6, 3RE60 HT 60 min RT; 7, 2205 MA 80EC; 8, 3RE60 HT 300 min
RT;9, 3RE60 MA 50C; 10, 3RE60 MA 80EC.

Fig. 3. Effect of sigma phase volume on the pitting potential of SAF 2205 and 3RE60 DSS in artificial seawater as a
function of seawater temperature (the SAF 2205 shows immunity to pitting attack at room temperature even under sigma
phase precipitation).

ration resistance with longer-term inappropriate the sigma phase. The effect of sigma phase on the
heat treatment exposure may be related to the localized corrosion of super-duplex stainless steel
higher depletion of Cr and Mo in zones next to in seawater has been previously studied by Wilms
272 H.M. Ezuber et al. / Desalination 207 (2007) 268275

et al. [17]. They reported that the initiation of

localized corrosion takes place next to the sigma
phase and the intensity of the corrosion attack
increases with increasing 800EC aging time.
Furthermore, the weakness of the passive film at
Cr-Mo depleted regions may also play a major
role in the film breakdown which leads to pit
initiation. The nucleation and propagation of
pitting corrosion are generally related to the
characteristics of the oxide film formed on
stainless steel alloy surfaces. Pastogi et al. have
reported that oxide films produced during weld-
ing, soldering and stress relieving operation
becomes less resistant to localized corrosion
attack [22].
The E-log i plots presented in Fig. 2 show that
the mill-annealed and heat-treated SAF 2205
alloy specimens exhibit typical passivity followed
by sharp increase in current density at distinctive
higher potentials. The specimens surface were
examined microscopically following polarization
test. No evidence of pitting corrosion was found
which indicates that SAF 2205 alloy is immune to
room temperature seawater pitting attack even
under sigma phase precipitation. The rise of
current density at high anodic potential was not
caused by pitting corrosion, but related to other
oxidation reaction. The resistance of this alloy to
pitting corrosion is undoubtedly due to the higher
percentage of chromium, molybdenum and nitro-
gen. These elements act in combination with one
another and the presence of these elements in
adequate concentrations usually results in an
increase in the pitting corrosion resistance. It has
been reported that the mechanisms providing
these benefits are complex, involving the enrich-
ment of chromium below the passive film, the
formation of a nitride layer at the film-metal
interface, and the formation of a ferrous molyb-
date in the outer regions of the passive film [23].
Although the presence of sigma phase causes
depletion in chromium and molybdenum to adja-
cent areas which become susceptible sites to
Fig. 4. Optical photographs of surface morphology of HT
(10 min.) SAF 2205 duplex stainless steel alloy specimen
etched in 10 M KOH (a 200) after the potentiodynamic
polarization experiment in artificial seawater at 50EC.
pitting attack, the results suggest that at room
temperature the pitting susceptibility of the heat
treated DSS alloys is dependent upon the alloy
composition, and in particular the percentage of
Cr, Mo (and N), rather than the volume fraction
of the sigma phase precipitation. The results
suggests that the SAF 2205 heat-treated samples
maintain sufficient surface coverage of Cr and
Mo in the Cr-Mo depletion areas and theses
elements control the pitting corrosion process at
these critical areas.
The effect of increasing solution temperature
on the pitting corrosion behavior of both alloys
can be seen by comparing the polarization curves
shown in Fig. 2. Increasing the solution tem-
perature to 50EC has shifted the anodic curves
negatively, Ep of alloy 3RE60 to lower potential
values while activating the pitting process of SAF
2205 (Fig. 4). The effect of raising seawater
temperature on the corrosion process is attributed
to the facilitation of the oxygen reduction (catho-
dic reaction) on the passive film, the activation of
 H.M. Ezuber et al. / Desalination 207 (2007) 268275 273

Fig. 5. Potential-current density behavior of as received and heat-treated (HT) alloys 3RE60 and SAF 2205 DSS in artificial
seawater at 80EC as a function of heat-treatment time. 1, 2205 MA; 2, 2205 HT 10 min; 3, 2205 HT 300 min; 4, 3RE60
MA; 5, 3RE60 HT 10 min; 6, 3RE60 HT 300 min.

Fig. 6. Optical photographs of surface morphology of HT (10 min.) SAF 2205 duplex stainless steel alloy specimen etched
in 10 M KOH (a 100) after the potentiodynamic polarization experiment in artificial seawater at 80EC.

aggressive ions and hence the creation of a higher
number of corrosion cells [24]. At 50EC, Fig. 3
shows that the mill-annealed SAF 2205 samples
suffer pitting attack at a potential value of
360 mV (SCE). Under inappropriate heat treat-
ment duration of 10 or 60 minutes the alloy
shows 30 mV negative shifts in pitting potential
(Ep occurred at 330 mV SCE). The 300-min HT
sample showed a pitting potential value of
255 mV (SCE) corresponding to 105 mV nega-
tive shift when compared to the mill-annealed
samples indicating that sigma is a service prob-
lem where longer-term exposure is involved.
Fig. 3 also shows that the presence of -phase
precipitation has negatively shifted the pitting
potential of the 3RE60 to lower values. While the
mill-annealed sample suffer pitting attack at
80 mV (SCE) the 10, 60 and 300-min HT
274 H.M. Ezuber et al. / Desalination 207 (2007) 268275
samples exhibited pitting at 45, 15 and !15 mV
(SCE) respectively. The results indicated that the
effect of increasing volume fraction of sigma
phase precipitation on Ep becomes more effec-
tual with longer inappropriate heat treatment
exposure.
Raising the temperature to 80EC further
decreases the seawater pitting potential for both
alloys with better corrosion resistance of the SAF
2205 (Figs. 2, 3 and 5). Although increasing the
solution temperature has activated the pitting of
HT alloys to attain more active potential values,
this shift in Ep becomes less pronounced as the
solution temperature is increased. Microscopic
examinations (Fig. 6) show that pits on HT SAF
2205 are taking place at the austenite-ferrite
boundaries, with the result that propagation
occurs more obviously into the ferrite phase. This
indicates the beneficial presence of 0.22% of
nitrogen since this element is preferentially par-
titioned to the austenite phase [25]. In conjunc-
tion with the residual chromium and molyb-
denum, nitrogen renders the austenite phase more
resistant to pitting than the ferrite phase [2527].
4. Conclusion
The seawater pitting corrosion of 3RE60 and
SAF 2205 DSS depends largely on the inappro-
priate heat treatment duration (volume fraction of
sigma phase precipitation) and test temperature.
The intensity of the pitting attack is markedly
increased with increasing seawater temperature
and/or inappropriate heat treatment duration with
better pitting corrosion resistance for the SAF
2205 alloy.
Although the 2205 DSS alloy showed immu-
nity to seawater pitting corrosion at room
temperature even when subjected to sigma phase
precipitation, this alloy exhibited susceptibility to
pitting attack at 50EC. The shift in pitting poten-
tial due to application of inappropriate heat
treatment is more effectual at longer-term heat-
treatment exposure.
Microscopic examinations revealed that pits
on HT SAF 2205 are taking place at the austenite-
ferrite boundaries, with the result that propa-
gation occurs more obviously into the ferrite
phase, indicating the beneficial presence of
0.22% of nitrogen.
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