Arabian Journal of Chemistry (2017) 10, S90–S94

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
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ORIGINAL ARTICLE

Effect of solution treatment on pitting behavior

of 2205 duplex stainless steel
H. Luo, X.G. Li 1, C.F. Dong *, K. Xiao 2

Corrosion and Protection Center, University of Science and Technology Beijing, Beijing 100083, China

Received 13 February 2012; accepted 12 June 2012

Available online 4 August 2012

KEYWORDS Abstract The effect of solution heat treatment on pitting behavior of 2205 duplex stainless steel
Heat treatments; was investigated by EDS, potentiodynamic polarization and SECM. The contrast experiments were
Duplex stainless steel; carried out on the original steel. The results demonstrate that for the original sample, when the
SECM; potential was at the open circuit potential, there were many pitting precursor areas, due to the local
Pitting breakdown of passive film on the surface, the pitting current fluctuations on the scale of pA. On the
contrary, after 1100 C solution treatment, the passive film was more stable than the original one.
Therefore, the solution treatment can markedly improve the pitting resistance of 2205 duplex stain-
less steel due to the reduction of pitting precursor areas.
ª 2012 Production and hosting by Elsevier B.V. on behalf of King Saud University. This is an open access
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1. Introduction obtained with approximately equal amounts of austenite and

2205 duplex stainless steel (DSS) with a ferrite/austenite has
been increasingly used for its attractive combination of
mechanical properties and corrosion resistance (Tsai and
Chen, 2000; Ezuber et al., 2007). The high corrosion resistance
of DSS is due to not only alloying elements such as Cr, Mo and
N, but also the microstructure. The best general properties are
* Corresponding author. Tel.: +86 10 62333931x518; fax: +86 10
62334005.
E-mail addresses: hongluo81@126.com (H. Luo), lixg2010@126.com
(X.G. Li), cfdong@ustb.edu.cn (C.F. Dong), xiaokui@sina.com (K.
Xiao).
1 variations in the conductivity, and chemical reactivity of so-
Tel.: +86 10 62333931x502; fax: +86 10 62334005.
2
Tel.: +86 10 62333931x522; fax: +86 10 62334005.
Peer review under responsibility of King Saud University.
Production and hosting by Elsevier
ferrite and the absence of the third phase, which can be formed
from ferrite after hot rolling without quick cooling.
There are many reports about the pitting corrosion resis-
tance of DSS (Moura et al., 2008; do Nascimento et al.,
2008) and also pointed out that the solution heat treatment
could improve the pitting corrosion. However, seldom expla-
nations focus on why the pitting resistance is improved after
the change of microstructure. Also there is not enough direct
evidence because of the limitation of experimental methods.
Scanning electrochemical microscopy (SECM) represents a
powerful scanning probe technique in that it can be used for
high-resolution topographic imaging, mapping microscopic
lid/liquid interfaces (Bard et al., 1989; Fushimi and Seo,
2001). In the field of corrosion, dissolution of iron, passivity
of iron and localized corrosion of stainless steels (Fushimi
et al., 1999; Williams et al., 1998; Paik et al., 2000), have been
investigated by SECM. Therefore, the local corrosion process
due to the solution treatment could be detected by SECM.

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Effect of solution treatment on pitting behavior of 2205 duplex stainless steel S91

In this paper, the effects of 1100 C solution heat treatment on

Table 1 The corresponding composite data of the single phase
pitting behavior of 2205 DSS in chloride solution environments
of 2205 DSS.
were investigated by potentiodynamic anodic polarization, en-
ergy disperse spectroscopy (EDS), and scanning electron micros- Status Microstructure Cr Ni Mo N PREN
copy (SEM). At the same time, the stability of passive film of 2205 Original a 23.84 5.52 3.45 0.05 36.03
DSS was studied by SECM by detecting the dissolved Fe2+ ions c 21.08 7.19 2.27 0.37 34.49
emanating from propagating metastable pits. Solution a 24.93 6.19 3.62 0.05 37.67
c 22.26 7.31 2.29 0.38 35.89
2. Experimental

The material used in this work was cut from a sheet of 2205
DSS supplied by Avesta Inc., with the chemical composition
(wt.%): C 0.014, Cr 22.39, Ni 5.68, N 0.17, Mo 3.13, Si 0.39, solution treatment
Mn 1.38, S 0.001, P 0.023 and Fe balance. The material’s solu- 1.5 original statement
tion heat treatments were held at 1100 C for 2 h under atmo-

Potential (V/SCE)
sphere and then cooled quickly in water. 1.0
The test solutions employed for the test were 0.1 mol/L EF-pit
NaCl. All the solutions were prepared from reagent grade Pitting of Ferrite
chemicals and Millipore-Q water. Before each measurement, 0.5 EA-pit
the solutions were purged with nitrogen gas for 1 h. All the
experiments were conducted at the room temperature. Each
0.0 Ecorr Passive
type of measurement was repeated at least three times.
Electrochemical measurements were performed with a
PAR VMP3 potentiostat. All potentials were referred to -0.5
-7 -6 -5 -4 -3 -2 -1 0 1
2
log current density (mA/cm )

Figure 2 Potentiodynamic polarization curves for 2205 duplex

stainless steel.

the saturated calomel electrode (SCE). Before electrochemi-

cal tests, the specimens were cathodically cleaned for
20 min at 800 mVSCE to remove the primary oxide film.
Specimens were immersed in the test solution 1 h prior to
each measurement in order to stabilize the open-circuit po-
tential. The potentiodynamic anodic polarization tests were
conducted, at a scanning rate of 1.5 mV/s, starting from
800 mVSCE and finally moved to the anodic direction.
The pitting potentials of austenite and ferrite were defined
as EA-pit and EF-pit.
SECM experiments were carried out on a M370 electro-
chemical workstation, including a scanning microprobe with
a tip, a 370 scanning control unit, a M236A potentiostat, a
M5210 lock-in amplifier and a video camera system. SECM
image was performed in a conventional four-electrode elec-
trochemical cell with a Pt microelectrode (10 lm) and a
modified glassy carbon (GC) plate as the working electrodes
(probe and substrate, respectively), a saturated calomel elec-
trode as reference electrode and a Pt wire as counter elec-
trode. The application of potential and the record of
current were done by a M236A potentiostat controlled via
SECM.
Before SECM measurements, the approach curves were
measured over the chosen scan area, and the tip was ap-
proached to the sample surface (z-approach curve). Then the
tip potential was kept at 0.6 VSCE in order to detect the
Fe2+ ions generating from the sample surface. The scan area
Figure 1 The microstructure of 2205 duplex stainless steel: (a)
is 1000 · 1000 lm. After tests the pitting morphology of the
original; (b) solution treated. (A: austenitic phase; F: ferritic
samples was observed by SEM.
phase).
S92 H. Luo et al.

(a) 16 16.00 (c) 10 10.00

11.00
12 8.000
8
Current /pA
6.000

Current /pA
6.000
8 1.000
6 4.000
-4.000
4
2.000

0 4
1000 1000
800 800

m
-4

m
600 2 600

/µ
0

/µ
200 0

ce
400

ce
200 400
400

an
400

an
200
X dista 600 600

st
200

st
nce/µm 800 X dista

di
di
1000 0 nce/µm 800 1000 0

Y
Y
(b) 16 16.00
(d) 10
10.00
11.00
12
7.625
Current /pA

6.000 8

Current / pA
8 5.250
1.000

6 2.875
4 -4.000

0.5000
0 4
1000
800 1000
/µm

-4 600 800
0 200

m
ce

400 2 600

/µ
400 0
an

ce
600 200 200 400

an
ist

800 400
X dista 600

st
200
Yd

nce/µm 1000 0

di
X dista 800
nce/µm 1000 0

Y
Figure 3 SECM images of 2205 duplex stainless steel surface after immersion in NaCl at the open circuit potential. (a) original state
(immediately); (b) after solution treatment (immediately); (c) original state (after 1 h immersion); (d) after solution treatment (after 1 h
immersion).

3. Results and discussion
3.1. The effect of microstructure and chemical composition
Fig. 1(a) and (b) represents metallographic images of the origi-
nal state (without solution heat treatments) and solution heat
treated samples. The etching solution was concentrated aqua
regia solution.
The austenitic phase (A) and ferritic phase (F) are shown in
Fig. 1. It clearly shows that the strips of austenitic phase and
ferritic phase are distributed alternately, and there is a small
amount of other phase particles in the original sample
(Fig. 1a). After 1100 C solution heat treatment, the austenitic
phase changed from strips to equiaxed blocks and the amount
of other phase particles decreased (Fig. 1b). These results indi-
cate that the solution treatment can influence the distribution
of the two phases and the amount of phase particles.
The corresponding composite data of the original samples
and solution treated samples are summarized in Table 1. As
can be seen from Table 1, for the original sample, Cr, Mo
and Si are higher in the ferrite, while Mn and Ni are higher
in the austenite. After solution treatment, the contents of Cr,
Mo and Ni increased in both the phases due to the decrease
of the second phase particles. This demonstrated that the solu-
tion treatment can also influence the distribution of Cr, Mo, N
and Ni in the phases of 2205 DSS.
The pitting behavior of 2205 DSS is closely related to the
composition of ferrite phase and austenite phase. Nitrogen
can significantly affect the distribution coefficients of Cr and
Mo in the two phases, making these elements transfer from
austenite to ferrite phase (Bliznuk et al., 2005). Nitrogen in
the two phases is calculated by means of the ThermoCalc com-
puter program. A common way to define the pitting resistance
of stainless steel is the pitting resistance equivalent number
(PREN). The higher the PREN, the better the pitting resis-
tance is. This parameter strongly depends on the content of
three most important elements Cr, Mo and N, according to
their influence on pitting:
PREN ¼ %Cr þ 3:3%Mo þ 16%N½11:
It is clear that the PREN for each phase could be calcu-
lated. The content of important elements, such as Cr, Ni,
Mo, and N, in austenite and ferrite phases for the two alloys
is shown in Table 1 together with the PREN for the two
phases. The results show that the solution treatment markedly
improved the value of PREN, indicating that the pitting resis-
tance of the sample enhanced by solution treatment.
Effect of solution treatment on pitting behavior of 2205 duplex stainless steel S93

3.2. The effect of polarization curves
Fig. 2 shows the potentiodynamic polarization curves of 2205
DSS in the original state and after 1100 C solution treatment.
As can be seen, on the cathodic branch of the curve, hydrogen
evolution reaction appears due to water electrolysis. On the
anodic part, an important feature of the polarization behavior
is the existence of two discrete pitting potentials. The sample is
passive when the potential was under 450 mVSCE. When the
potential is higher than 450 mVSCE, pitting occurred in the
austenite phase, while the ferrite remained passive. However,
when the potential reached to 1050 mVSCE, pitting occurred
in both austenite and ferrite phases.
The EA-pit for original state and after solution treatment is
nearly the same. Therefore, the pitting resistance of 2205 DSS
mainly depends on the pitting resistance of ferrite. Hussain (do
Nascimento et al., 2008; Hussain and Robinson, 2007; Symni-
otis, 1990) also confirmed the differences in the stability of the
passive films on the two phases of 2205 DSS, and the pits are
preferentially nucleated in the c/d boundaries. These conclu-
sions are all corresponding with the PREN results.
3.3. The stability of the passive film and pitting precursor area
are related to such nucleation of pits occurring on the samples.
The peaks (González-Garcı́a et al., 2004) in the images are the
areas, where the oxide film is broken. There can be no tip reac-
tion of the simultaneously dissolving Cr3+or Ni2+. The only
possible reaction at the tip is therefore the oxidation of Fe2+to
Fe3+ on the SECM tip. Fe2+ was released from the dissolving
point on surface, where it may be a pit precursor.
As is shown in the Fig. 3(a) and (b), the amount of the cur-
rent peaks on the original sample is more than that after solu-
tion treated. This indicated that the protective property of the
passive film on the original sample is weaker than that after the
solution treated sample.
Fig. 3(c) and (d) provide images obtained after immersing
for 1 h in test solution. Obviously, the background currents
tend to be flat. The current peaks in Fig. 3(d) is less than that
in Fig. 3(c), indicating that the solution treatment markedly
enhanced the pitting resistance of the sample, this also indi-
cated that with the immersion time being prolonged, the
destruction of chloride and the reparation of the passive film
constantly happened and reach a new state.
The deleterious tertiary phases, such as sigma, chromium
carbides and nitrides, exist as a chromium depleted zone,
which inclines to be corroded first. When deleterious phases

The stability of the passive film is measured by the SECM.

Based on the voltammogram characterization of the Pt ultra
microelectrode in the testing solution, the probe potential is
set at about 600 mVSCE for maximal collection of the local
electrochemical current. I =I
3 is used as the redox mediator
and the tip-interface distance is determined by moving the Pt
ultramicroelectrode slowly to the sample surface. In the KI
solution, iodide ions in the oxidation reaction occur on the
probe. The reaction is as follows:
3I ! I
3 þ 2e ð3:1Þ
Reactions that occurred on the sample surface are:
Fe  2e ! Fe2þ ð3:2Þ

Fe2þ þ I 
3 ! I þ Fe
3þ
ð3:3Þ
According to feedback and generation/collection mode of
SECM, the reduced iodide ions will be oxidized again on the
probe. When the Pt microelectrode closes to the conductor sur-
face, positive feedback occurs. As the distance increases, the
current signal begins to fluctuate. Therefore, the distance be-
tween the substrate and the probe is ultimately determined
within 10 lm.
Fig. 3 displays the SECM three-dimension images of the
original and solution treated samples in 0.1 M NaCl solution
at the open-circuit potential. The images show clearly different
current levels in different active areas. The topography seems
somehow rough and a number of peaks projecting into the
anodic direction of spatial extent a few micrometers, died
down in a short time. And most of them lasted less than the
time in which they can complete a line scan.
In the test solution, chloride ions will be adsorbed on sur-
face film, undermining the integrity of passive film and leading
to the nucleation of pits. Nucleation of pits can hardly be de-
tected by conventional electrochemical measurements, but it
can be easily detected by SECM. The current peaks in Fig. 3 Figure 4 The SEM of 2205 duplex stainless steel after polari-
zation (a) Original sample (b) Solution treatment sample.
S94
are worn away, the passive film on the metal surface has not
yet dissolved, leading to the even deeper corrosion at the chro-
mium depleted zone (Kajimura et al., 1995). But, after the
solution treatment, the deleterious phase dissolved and also
the chromium depleted zone disappeared.
Generally speaking, at the open-circuit potential, the pas-
sive film is stable in the chloride solutions with low concentra-
tion. However, the SECM results, which showed that the
presence of chloride ions in the electrolyte gives rise to surface
heterogeneities, disagree with the above statement. These may
be due to the inhomogeneous absorption of Cl ions. The Cl
ions incline to be adsorbed at the defective places, like cracks
and dislocations. The Cl ions adsorbed on the surface or
incorporated into the passive film can be detrimental to film
stability, leading to the initiation of pitting.
3.4. Surface morphology
Fig. 4 shows the surface morphologies of the samples after
electrochemical tests. Due to the less protective ability of the
passive film, there are more pits on the original samples than
that after solution treated.
However, it can be seen that the number of pits on the trea-
ted sample is less, the size of the pits is much bigger than that
on the original sample. This indicates that pitting inclines to
develop at the point where pits have already happened, that
is, exaggerate the existing pits instead of forming new pits on
the treated sample.
4. Conclusions
(1) The alloy element content in the ferrite and the austenite
is not the same in the original state and treated state.
The 2205 DSS after solution treatment has a higher pit-
ting resistance than the original state.
(2) SECM clearly detected the effect of solution treatment
on the pitting corrosion of 2205 DSS. The results
showed that at the open circuit potential, more current
peaks, corresponding to the pitting precursors, were
observed on the original sample. After the solution
treatment, the amount of current peaks markedly
decreased. It demonstrated that the solution treatment
enhanced the pitting corrosion resistance of 2205 duplex
stainless steel.
(3) There are more pits on the original samples than the
solution treatment sample, though the pits are bigger
on the latter surface. The explanation is that pitting
inclines to develop at the point where pits have already
happened on the treated sample, instead of forming
the new pits as happened on the original sample.
H. Luo et al.
Acknowledgements
This work is supported by The Fundamental Research Funds
for the Central Universities (No. FRF-TP-11-006B) and The
National Natural Science Foundation of China
(No.51131005).
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