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Inuence of nickel additions on the corrosion behaviour of low nitrogen 22%

Cr series duplex stainless steels


J.H. Potgieter
a
, P.A. Olubambi
a,
*
, L. Cornish
a
, C.N. Machio
a
, El-Sayed M. Sherif
b
a
DST/NRF Centre of Excellence in Strong Materials, School of Chemical and Metallurgical Engineering, University of the Witwatersrand,
Private Bag 2050, WITS, Johannesburg, South Africa
b
DST/NRF Centre of Excellence in Strong Materials, School of Physics, University of the Witwatersrand, Johannesburg, South Africa
a r t i c l e i n f o
Article history:
Received 24 October 2007
Accepted 8 May 2008
Available online 4 July 2008
Keywords:
Duplex stainless steel
Nickel
Microstructure
Phase modication
Corrosion
a b s t r a c t
Four 22% Cr duplex stainless steel alloys containing varying nickel contents of approximately 5%, 7%, 9%
and 13% were melted in a vacuum induction furnace, hot rolled, solution annealed and water quenched.
Their corrosion behaviour was investigated in sulphuric acid and sodium chloride solutions using poten-
tiodynamic polarization and chronoamperometric techniques. Increasing nickel contents have an appre-
ciable inuence on the observed corrosion behaviour. Polarization curves show similarities in the
uniform corrosion behaviour of the alloys in the various solutions, but signicant differences in their pit-
ting resistance in chloride environments. Alloy 2209 (22% Cr 9% Ni) generally exhibited the highest
resistance to uniform corrosion, while alloy 2213 (22% Cr 13% Ni) displayed the best pitting corrosion
resistance. X-ray diffraction analysis of the surfaces of the alloys after corrosion in the different media
revealed different corrosion products. Scanning electron micrographs revealed that the alloys were differ-
ently attacked by chloride ions, with different pit depths and morphologies. The corrosion behaviour
exhibited by the alloys was attributed to the inuence of nickel on phase modication, microstructural
renement, and the types of lms formed in different environments. Uniform corrosion behaviour of
the alloys was concluded to be predominantly controlled by phase composition and ratio, while pitting
resistance was chiey controlled by an alloys nickel contents.
2008 Elsevier Ltd. All rights reserved.
1. Introduction
The overall cost and environmental implications of corrosion
problems has become a major challenge to engineers in the ght
against corrosion and the quest to reduce economic loss. Several
approaches, including cathodic protection, coatings, and corrosion
inhibitors have been employed to mitigate corrosion. However,
due to the fact that these approached are external, attention should
also be focused on the selection of proper corrosion resistant alloys
for specic industrial applications. Among the alternative corro-
sion resistant alloys, improvements over the years have been cen-
tred on the development of duplex stainless steels [1]. This is
because duplex stainless steels combine the advantages of both
ferritic and austenitic stainless steels [2]. It offers a combination
of properties, such as particularly corrosion resistance in hot corro-
sion environments containing chloride ions, mechanical strength
and ductility, abrasion resistance, and weldability.
Duplex stainless steels are employed in a variety of applications
in the oil and gas industries [1,3,4] where carbon dioxide corrosion
easily causes the failure of pipelines [5], pulp and paper plants [6],
chloride containing process uids and ammonium carbamate solu-
tions [7], mining and minerals processing industries, phosphatic
and urea based fertiliser plants [8], and in numerous other chemi-
cal industries. Although they clearly offer useful benets over
austenitic and ferritic grades, duplex stainless steels are observed
to be susceptible to crevice corrosion and stress corrosion cracking,
especially in seawater, when components are submerged, and in
other chloride environments. Hence, cathodic protection is often
employed in the oil and gas industries when used at higher opera-
tional temperatures and materials are externally coated to reduce
anode consumption [4].
Corrosion and other mechanical properties of duplex stainless
steels are directly dependent on its microstructure and phase.
According to Vignal et al. [9], quantitative information on the prop-
erties and electrochemical behaviour of individual phases of duplex
stainless steel are useful parameters in understanding and assessing
their corrosion mechanisms. Therefore, the modication of the
microstructures and phases within duplex stainless steels would
be very effective in improving their overall corrosion resistance
and mechanical properties required in service. A reported effective
modicationapproachis the alloyingof these steels withsome addi-
tion of nickel. The addition of nickel to duplex stainless steels plays
animportant roleinmaintaininganaustenite/ferritebalance, as aus-
tenite promoter and improver of pitting resistance [10].
0010-938X/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2008.05.023
* Corresponding author. Tel.: +27 011 7177566; fax: +27 011 403 1471.
E-mail addresses: peter.olubambi@students.ac.za, polubambi@yahoo.com (P.A.
Olubambi).
Corrosion Science 50 (2008) 25722579
Contents lists available at ScienceDirect
Corrosion Science
j our nal homepage: www. el sevi er . com/ l ocat e/ cor sci
The additionof nitrogenhas beenobservedto be analternative to
nickel, due to its effective nickel-substituting potential for austenite
formation. Nitrogen increases strength, and improves the resistance
of duplex stainless steel to crevice and pitting corrosion in chloride
environments. However, nitrogen has a major drawback of limited
solubility in steels. Its solubility can be increased by the addition of
manganese and molybdenum. Although they increase solubility,
high molybdenum contents can lead to the formation of d-ferrite
and r-phase which decrease toughness and corrosion resistance.
Hnninen et al. [11] observed that higher chromium and nitrogen
withlownickel superduplex stainless steel are very difcult to man-
ufacture via traditional metal working practices, because they are
prone to hot cracking in forging and macrosegregation in casting.
Increasing nitrogen additions can also cause chromium nitride pre-
cipitation, especiallyinthe heat affectedzoneinweldedjoints. Chro-
mium nitride decreases the corrosion resistance as it could cause a
chromium depleted zone which could result in localized corrosion
attack [12]. There is therefore a limit to which nitrogen addition
can be used to substitute nickel.
A number of research studies on the addition of nickel to im-
prove the corrosion resistance of duplex stainless steels have been
reported [10,1315]. However, these studies were mostly centered
around the inuence of nickel additions on welds. The investiga-
tion reported by Tavara et al. [10], concentrated on the susceptibil-
ity of welds to corrosion fatigue, while that of Muthupandi et al.
[13] was on the microstructure and mechanical properties of
welds. The 22% Cr duplex stainless steels, especially 2205, have po-
tential for many industrial applications, as they provide superior
pitting and crevice corrosion resistance in many corrosive media.
Although nickel improves the corrosion resistance of stainless
steel, little attention has been given to the possibilities of improv-
ing the corrosion resistance of the 22% Cr duplex stainless steel
through nickel additions.
It is well known that the ferrite microstructure is better resis-
tant against chloride attack than the conventional austenitic
microstructures. As there were limited reports in literature on
the effects of nickel addition on the corrosion behaviour of various
duplex stainless steel [14,16,17], and little attention has been paid
to the varying austenite: ferrite microstructural ratios on general
and localized corrosion behaviour of duplex stainless steels, it
was decided to investigate the effects and interplay of both these
two variables in a 22% Cr duplex stainless steel. For this purpose,
a base 22% Cr duplex stainless steel with 5% nickel (and very little
nitrogen) was modied with further additions nickel, which re-
sulted in subsequent differences in ferrite: austenite phase ratios.
Choosing a base alloy with very low nitrogen content allowed
the unhindered observation on the effects of nickel on the general
corrosion behaviour of the various duplex alloys prepared. The
simultaneous variation in the ferrite: austenite phase ratios with
increasing nickel additions not only enables one to estimate this ef-
fect on the general corrosion behaviour of the duplex stainless
steel investigated, but also to study the effect and the differences
in the localized corrosion resistance of the two phases on pitting
corrosion behaviour of the resultant duplex alloy as their ratios
changed in the microstructure with increasing nickel contents.
2. Experimental details
The alloys used in this investigation were all melted in a vac-
uum induction furnace. Chemical analyses were performed by
XRF spectrometry, Leco and ICP measurements and the results
are given in Table 1. Each cast ingot was hot rolled into a plate with
a thickness of between 3 mm and 6 mm, then solution annealed at
1100 C for an hour and water quenched. No deliberate nitrogen
additions were made to any of the alloys, so the varying nickel con-
centrations caused a different proportion of austenite to ferrite
phase in each of the alloys. In the 2205 alloy, the austenite phase
was approximately 15%, in 2207 it was about 35%, in 2209 it was
equal in ratio to the ferrite phase, i.e. 50%, and it increased to
around 80% in the 2213 alloy.
The specimens were cold mounted in resins, and they were left
to dry for 12 h at room temperature. Specimens for microstructural
observation were mechanically ground with silicon carbide papers
from 220 down to 1000 grade. They were polished with several
grades of diamond pastes, rinsed in distilled water, degreased with
acetone, and electroetched with oxalic acid to reveal the details of
their microstructures. Microstructural observations were per-
formed using an Axiotech microscope equipped with an AxioCam
MRc digital camera.
Samples for electrochemical analysis were prepared by attach-
ing an insulated copper wire to one face of the sample using an alu-
minum conducting tape, and cold mounted in resin. The surfaces of
the samples were ground with silicon carbide papers from 220
down to 600 grade, washed with distilled water, degreased with
acetone and dried in air. In order to prevent the possibility of cre-
vice corrosion during measurement, the interface between sample
and resin were coated with Bostik Quickset, a polyacrelate resin.
All samples were immersed in electrolyte not more than 1 h after
each surface preparation.
Electrochemical corrosion behaviour of the samples was investi-
gated using potentiodynamic polarization measurements in 1 Mso-
dium chloride and 1 M sulphuric acid solutions, while pitting
behaviour was studied using pitting scans in 3.5% sodium chloride
solution. The electrochemical cell was a conventional three-elec-
trode cell comprising the sample, a silver/silver chloride, 3 M KCl,
reference electrode, and graphite counter electrode. All electro-
chemical measurements were made at room temperature
(25 1 C) with an Autolab potentiostat (PGSTAT20 computer con-
trolled) using the general purpose electrochemical software (GPES)
version 4.9. The software determined the corrosion potential (E
corr
),
corrosioncurrent (I
corr
) and corrosioncurrent density (i
corr
) fromthe
polarization experiments, and calculated the corrosion rates.
Before potentiodynamic polarization, working electrodes were
immersed in the electrolytes for at least 20 min for stabilization
of the open-circuit potential (OCP). Polarization curves were mea-
sured at a scan rate of 1.6 mV/s starting from 500 mV to
1500 mV, while pitting scans were measured at a scan rate of
3 mV/s. Currenttime behaviour of the alloy displaying the highest
resistance to uniform corrosion was studied in 3.5% sodium chlo-
ride and in 1 M sulphuric acid under an applied potential of
300 mV. Currenttime behaviour of all the alloys was also studied
in 3.5% sodium chloride solutions at the same applied potential.
After each scan, the electrolytes were replaced. The samples were
polished after each experiment, rinsed in water and washed with
acetone to remove the products that might form on the surface
that could affect the following measurement. All tests were carried
out in triplicate to ensure reliability, and a fairly good reproducibil-
ity was achieved.
The nature of corroded products on the surface on the alloys
was analyzed using X-ray diffractometry. Pit morphologies on
the surfaces of the corroded samples immersed in 3.5% sodium
chloride solution were examined using SEM.
3. Results and discussion
3.1. Microstructural observation
The typical micrographs of the microstructures of the four
investigated duplex stainless are shown in Fig. 1 The gray region
in the micrographs corresponds to the ferritic phase (a) while
J.H. Potgieter et al. / Corrosion Science 50 (2008) 25722579 2573
the whiter regions correspond to the austenitic phase (c). It can be
seen that the amounts of austenitic phases increased as the nickel
contents of the steel increased. Grain sizes also increased as nickel
contents increased.
The increase in the austenitic phases as nickel contents in-
creased as observed in the micrographs conrms that nickel pro-
motes the formation of austenite phases in duplex stainless
steels [18]. This was also conrmed by the analysis of the alloys
shown in Table 1. Transformation in grain size observed with in-
creased in nickel content could be an indication that nickel addi-
tion causes renement in grain-size. This was quite evident as
seen in the relatively equiaxed microstructures of the 2213 steel.
This grain renement could be attributed to the fact that when
the percentage of austenite is higher than ferrite and a diffusion
interface could emerge [19] at grain boundaries which might mod-
ify the structure, as well as the properties. Increased austenitic
phase might in turn result in a nickel concentration gradient from
austenite to ferrite phase which could thereby lead to an interdif-
fusion zone promoting grain renement. A similar situation was
observed by Campos et al. [19] where increased austenite was re-
ported to improve the microstructure of duplex stainless steel pro-
duced by powdered metallurgy.
Although there were differences in the carbon contents of the
various alloys investigated, as indicated in Table 1, the overall car-
bon content in all the materials was very low and unlikely to affect
the corrosion behaviour observed to any signicant extent. An in-
crease in the carbon content from 0.01 to 0.03 should not at such
extremely level have any signicant effect on the corrosion resis-
tance of the investigated alloys. It should only play a role if it re-
sulted in increase carbide precipitation along the grain
boundaries, and no such phenomenon has been observed in the
microstructures of the various duplex alloys.
3.2. Electrochemical behaviour
Fig. 2 shows the polarization curves obtained in a 1 M sulphuric
acid solution. Polarization curves displayed similar trends for all
the alloys, with a small but distinct activepassive transition in
all the samples. Alloy 2205 showed the least uniform corrosion
resistance while alloy 2209 displayed the best resistance to uni-
form corrosion. Although the polarization curves were very similar,
the passive region displayed by the alloys showed slight incre-
ments as the amounts of nickel addition increased. This region
was within the potential range of 10001150 mV. Alloy 2205 de-
picted the smallest passive region, while alloy 2213 had the largest
passive region, followed by 2209. This corresponds well with pre-
vious observations by Azuma et al. [14] that increasing nickel con-
tents lowers the depassivation pH of duplex stainless steels in
acidic media. The polarization curves obtained for the alloys in
1 M sodium chloride solutions are presented in Fig. 3. There was
apparently no noticeable active-to-passive transition behaviour
in all the alloys. Alloys 2207, 2209 and 2213 showed similar and
closely related corrosion behaviour. It was observed that they un-
dergo very severe pitting corrosion, but alloy 2213 clearly showing
distinctly better pitting resistance as compared to others. This
could be due to combined increased resistance caused by an in-
crease in nickel content [16,14], as well as the large anode (c) small
cathode (a) effect regarding pitting corrosion resistance differ-
Table 1
Chemical composition of materials studied (mass%)
Alloy Austenite (%) Ferrite (%) Fe Cr Ni Mo Si N C
2205 15 85 Balance 21.3 5.05 2.73 0.04 0.002 0.01
2207 35 65 Balance 21.7 6.98 2.83 0.05 0.003 0.02
2209 50 50 Balance 22.0 9.07 2.81 0.07 0.006 0.03
2213 80 20 Balance 22.1 13.14 2.79 0.04 0.003 0.03
Fig. 1. Optical micrographs of the four 22% Cr duplex stainless steels showing ferritic phase (grey regions) and austenitic phase (white regions) compositions.
(Magnication 200).
2574 J.H. Potgieter et al. / Corrosion Science 50 (2008) 25722579
ences between the two phases. The corrosion of these alloys was
generally lower in 1 M sodium chloride solution than in 1 M sul-
phuric acid solution. The passive regions of the alloys in sodium
chloride solution were observed to be much smaller than in sul-
phuric acid solution.
The results for the corrosion potentials, corrosion current, cor-
rosion current densities, and the corrosion rates that were derived
from the electrochemical tests for the samples in the different
solutions are summarized in Table 2. In 1 M sulphuric acid solu-
tion, the corrosion potential was generally observed to increase
with increasing nickel contents. It is however observed that in so-
dium chloride media, the corrosion potential initially increased
with nickel additions up till 2209, but remain nearly the same or
slightly decreased with 2213. These observations indicated that
2205 is the most susceptible to corrosion in all the media investi-
gated. The corrosion current, corrosion current density, and corro-
sion rates, obtained from the polarization curves, for all the alloys
did not show wide differences in both media, except for 1 M so-
dium chloride solution where 2205 had a much lower corrosion
potential and smaller resistance than the others. It was noted that
the corrosion current density and corrosion rates decreased with
increasing nickel contents up till 2209 in chloride medium. Alloy
2213 would have been expected to be the most resistant to uni-
form corrosion due to its highest nickel contents, but 2209 was ob-
served to perform best. In sulphuric acid solution, alloy 2213 was
only second to 2209, while alloy 2213 and 2207 behaved similar
in chloride media. The results showed that the alloys corroded
most in sulphuric acid solution. These results indicated that it is
not only the nickel content, but probably also the microstructure
and a:c phase ratios, which inuence the observed behaviour.
These results conrm those of Yau and Streicher [15] and Tsai
and Chen [20] who observed the effects of the a/c couple on the
corrosion behaviour of duplex stainless steels in acidic media.
To assess the pitting corrosion behaviour of the alloys in an
environment similar to sea water, pitting scans were performed
on the samples in 3.5% sodium chloride solution. The pitting
behaviour presented in Fig. 4 and the electrochemical parameters
summarized in Table 3 showed that alloy 2213 displayed outstand-
ing pitting resistance as compared with the other alloys. The high-
est pitting resistance of alloy 2213 could seem contradictory to the
fact that it contains the most austenite phase, the less resistant of
the two phases against chloride attack. Its superior pitting resis-
tance however, can be ascribed to its increased amounts of nickel
dominating its resistance against pitting corrosion rather than
the amounts of austenitic phase. Alternatively, the partitioning of
the nickel to the austenite phase [21] increase its content in this
phase to a high enough value that its starts to display the same
resistance against chloride attack than one encountered in the high
nickel content (P30%) austenitic alloys. As nickel contents in-
crease, pitting and repassivation potentials increase, while corro-
sion potential was shifted to a more positive value. This was also
observed by Munoz et al. [22] in their investigation of localized
corrosion of high nickel content stainless steels. On the other hand,
corrosion current, current density and corrosion rate decreased
with increasing nickel contents up till 2209. It was very obvious
that increased nickel contents elevated the onset of the pitting po-
tential from where an increase in pitting corrosion occurred. The
benecial effects of nickel on the increase of the passive region
was observed by Tavara et al. [10] to have resulted from an enrich-
ment of nickel in the passive lm.
The chronoamperometric behaviour of alloy 2209 that exhib-
ited highest resistance to uniform corrosion in sulphuric acid and
sodium chloride is shown in Fig. 5. In sodium chloride medium,
current steadily increased up till the 2000th second after which
it started to decrease, but began to uctuate at the 2500th second.
In sulphuric acid medium on the hand, current steadily decreased
until the 2800th second after which it became steady. This con-
rmed that the alloyed pitted in 3.5% sodium chloride but passiv-
ated in sulphuric acid solution. The chronoamperometric
behaviour of the alloys in 3.5% sodium chloride shown in Fig. 6 re-
vealed that current decreased as nickel addition increased. Current
was steady for alloy 2213 throughout the experiment, but in-
creased for the remaining alloys with alloy 2205 displaying the
highest current. This indicates that low nickel alloys undergo more
pitting as compared with the higher nickel content alloys.
X-ray diffraction analysis of the products formed on surfaces of
the alloys after corrosion in sulphuric acid conrmed the presence
of nickel sulphide, nickel chromate, chromium sulphide and chro-
mium oxide layers. It is not clear whether the nickel and chromium
sulphides resulted from precipitated sulphide in the alloy micro-
structure or from the reduction of sulphuric acid. In 3.5% sodium
chloride solution however, nickel chromium oxide, nickel (II)
oxide, nickel (IV) oxide, chromium (II) oxide, and chromium (VI)
oxide were detected on the surface of the corroded product. The
SEM micrographs of the corroded surface immersed in 3.5% sodium
chloride solution presented in Fig. 7 revealed that the alloys were
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.00E-09 1.00E-07 1.00E-05 1.00E-03 1.00E-01
Current density (A/cm )
2
P
o
t
e
n
t
i
a
l

(
m
V
)
2209
2213
2207
2205
Fig. 2. Polarization curves for the 22% Cr duplex stainless steels alloys in 1 M
sulphuric acid solution. [Scan from500 mV to 1500 mV at a scan rate of 1.6 mV/s].
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.00E-10 1.00E-08 1.00E-06 1.00E-04 1.00E-02 1.00E+00
Current density (A/cm)
P
o
t
e
n
t
i
a
l

(
m
V
)
2213
2207
2209
2205
Fig. 3. Polarization curves for the 22% Cr duplex stainless steels alloys in 1 M
hydrochloric acid solution. [Scan from 500 mV to 1500 mV at a scan rate of
1.6 mV/s].
J.H. Potgieter et al. / Corrosion Science 50 (2008) 25722579 2575
differently attacked by chloride ions. The amounts and depths of
pits formed on the alloys decreased as nickel contents in the alloys
increased. Alloy 2205 had very deep and elongated pits, while alloy
2213 had none but was covered with precipitates.
The response of these alloys in different environmental condi-
tions could be presumed to be controlled by metallurgical factors,
including alloy composition, microstructure and partitioning of
elements to the phases. Alloy composition alters microstructure
and phases in a variety of ways. As it is well established, a nickel
addition improves the corrosion resistance of stainless steel in
many corrosive media [10,14,16,17]. The variations in grain sizes
and balance/imbalance of phase composition factors jointly inu-
ence their responses in the environments. The observed uniform
corrosion behaviour of the alloys could be assumed to be predom-
inantly controlled by phase composition while pitting resistance
was controlled by their nickel contents.
Table 2
Corrosion data obtained from the electrochemical tests
Corrosion media Alloy type E
corr
(V) I
corr
(A/cm
2
) i
corr
(A) Corr rate (mm/yr)
1 M H
2
SO
4
2205 0.289 1.3E-5 1.1E-5 1.6E-1
2207 0.260 1.0E-5 2.5E-6 1.2E-1
2209 0.244 8.1E-6 2.2E-6 0.9E-2
2213 0.237 1.0E-5 7.4E-6 1.2E-1
1 M NaCl 2205 0.391 2.3E-6 6.9E-7 3.8E-2
2207 0.281 1.2E-7 3.3E-8 1.4E-3
2209 0.281 1.0E-7 2.8E-8 1.2E-3
2213 0.282 2.6E-7 7.9E-8 3.1E-3
-0.5
-0.3
-0.1
0.1
0.3
0.5
0.7
0.9
1.1
1.3
1.00E-10 1.00E-08 1.00E-06 1.00E-04 1.00E-02 1.00E+00
Current density (A/cm
2
)
P
o
t
e
n
t
i
a
l

(
m
V
)
2205
-0.5
-0.3
-0.1
0.1
0.3
0.5
0.7
0.9
1.1
1.3
1.00E-10 1.00E-07 1.00E-04 1.00E-01 1.00E+02
Current density (A/cm
2
)
P
o
t
e
n
t
i
a
l

(
m
V
)
2207
1.00E-12 1.00E-10 1.00E-08 1.00E-06 1.00E-04 1.00E-02 1.00E+00
Current density (A/cm
2
)
2209
1.00E-08 1.00E-06 1.00E-04 1.00E-02 1.00E+00
Current density (A/cm
2
)
2213
-0.5
-0.3
-0.1
0.1
0.3
0.5
0.7
0.9
1.1
1.3
P
o
t
e
n
t
i
a
l

(
m
V
)
-0.5
-0.3
-0.1
0.1
0.3
0.5
0.7
0.9
1.1
1.3
P
o
t
e
n
t
i
a
l

(
m
V
)
Fig. 4. Pitting behaviour of the 22% Cr duplex stainless steels alloys in 3.5% sodium chloride solution. [at a scan rate of 3 mV/s].
Table 3
Pitting behaviour of the alloys in 3.5% NaCl
Types E
corr
(mV) i
corr
(A) I
corr
(A/cm
2
) Corr rate (mm/yr) E
P
(mV)
2205 280 6.26E-7 8.69E-7 1.01E-2 415
2207 261 1.49E-7 6.47E-7 7.52E-3 455
2209 257 6.75E-9 1.29E-8 1.50E-4 560
2213 232 1.69E-7 2.56E-7 2.98E-3 1143
2576 J.H. Potgieter et al. / Corrosion Science 50 (2008) 25722579
As observed in the microstructures of the alloys (Fig. 1), nickel
additions affected the grain sizes and grain boundaries. High nickel
contents led to an increase in the coarseness of the grain sizes and
a corresponding decrease in grain boundaries. Since local corrosion
events usually start at electrochemical active sites such as grain
boundaries [23], it is therefore believed that lower corrosion rates
observed in alloys containing higher nickel contents was due to
lower amounts of electrochemical active sites occurring at these
grain boundaries. Increasing the amounts of nickel to 13.14%
would have been expected to make alloy 2213 the most resistance
to uniform corrosion. However, it was observed in Figs 24 that
2209 had a better resistance to uniform corrosion in the solutions
studied.
The difference in the responses of these alloys to uniform corro-
sion could be attributed to the differences in their phase composi-
tions. Nickel being a strong austenite former was observed to
either maintained or caused a shift in the ferrite/austenite balance
in the alloys. The ferrite/austenite composition in 2209 was 50/50,
while 2213 was 20/80. The implication of this imbalance in the
phases might probably be that 2213 would behave partially
austenitic. The austenitic behaviour could presumably result in a
decrease in the resistance of the alloy to uniform corrosion in com-
parison with the duplex structure [24]. It might possibly result in
selective dissolution of the phases and therefore lead to a slightly
lower uniform corrosion resistance of 2213 as compared to 2209
having a perfect duplex phase of 50/50 ferrite/austenite balance.
Ferrite would be anodic towards the austenite, so while the ferrite
phase increases from 20% (in 2213) to 85% (in 2205), there is a
gradual decrease in the corrosion resistance of the duplex alloys.
The 2209 with the equal balance between the two phases displays
the best resistance because the galvanic effects are balanced. In
2213, the small anode of ferrite (20%) compare to the large cathode
accelerates the corrosion compared to the 2209 alloy. This was also
conrmed by previous work from both Yau and Streicher [15] and
Tsai and Chen [21].
The combined increased nickel content and the larger ferritic
anode percentage compared to the smaller cathode austenite con-
tents dominate the corrosion resistance behaviour up to alloy
2209. The galvanic interactions are therefore prominent in alloys
2213 and 2205, and less signicant in 2207 and 2209, whose
behaviours in all media are very similar. The optimal resistance
of alloy 2209 to uniform corrosion could therefore be attributed
to be equilibrium in the ratio of ferrite to austenite. Improvement
in the uniform corrosion resistance of alloy 2213 over 2205 could
therefore be attributed to higher percentage of nickel in 2213
and its rened and equiaxed microstructure.
Increasing nickel content could also accelerate the formation of
the lms formed on the surfaces as revealed by XRD studies. These
lms, can be very stable and passive and could increase the alloys
resistance to corrosion. According to Kish et al. [25], nickel atoms
in the stainless steel would tend to catalyze the reduction of sul-
phuric acid molecules in concentrated sulphuric acid and anodi-
cally dissolve with the formation of nickel sulphide deposit, in a
manner analogous to nickel, according to the simplied overall
reaction Eq. (1):
4Ni 4H
2
SO
4
3NiSO
4
NiS 4H
2
O 1
The nickel sulphide formed could have created a passive layer
that increased alloy passivity in the passive region. Kish et al.
[25] attributed the passivation resulting from nickel to the fact that
nickel promotes the formation of nickel sulphide during the passiv-
ation induction stage, which depolarizes the cathodic reduction of
undissociated sulphuric acid (through an increase in surface area)
to a level that provides the current required to stabilize the passive
chromium-rich oxide lm. According to Kish et al. [26], the catho-
dic reduction of concentrated sulphuric acid (probably to SO
2
Eq.
(2) at the passive region) usually takes place on the sulphide as
soon as sufcient nickel sulphide is nucleated.
H
2
SO
4
2H

2e

SO
2
2H
2
O 2
This could thereby increase the exchange current and might
produce mixed potential in the passive range, and caused the pas-
sive lm so formed at this potential to probably passivate chro-
mium alloys [17]. As the sulphuric acid in this investigation was
diluted, it is more likely that the nickel chromate and chromium
oxides detected by XRD caused the passivation of the stainless
steel surfaces. Although, small amounts of nickel and chromium
sulphides were detected by XRD analysis, it could originate from
alloy production techniques and inclusions in the material itself.
It is unlikely that the dilute sulphuric acid was reduced, but for
absolute clarication, this will need to be investigated further.
It was observed that increasing amounts of nickel did not abso-
lutely correspond to increasing the uniform corrosion resistance of
alloy 2213. Its distinct pitting resistance in sodium chloride solu-
tion and relatively longest passivity range in sulphuric acid solu-
tion could be ascribed to its highest amounts of nickel. The
ability of the high nickel containing alloy i.e alloy 2213 to exhibit
excellent pitting resistance in chloride environments, could be
attributed to the type of the stable passive nickel oxide layer as
0.00E+00
5.00E-05
1.00E-04
1.50E-04
2.00E-04
2.50E-04
3.00E-04
0 600 1200 1800 2400 3000 3600
Time (seconds)
C
u
r
r
e
n
t

d
e
n
s
i
t
y

(
A
/
c
m
2
)
1M H S O
2 4
3.5% NaCl
Fig. 5. Chronoamperometric behaviour of 2209 in 3.5% NaCl and 1 M H
2
SO
4
under
applied potential of 300 mV.
-1.00E-04
4.00E-04
9.00E-04
1.40E-03
1.90E-03
2.40E-03
2.90E-03
0 600 1200 1800 2400 3000 3600
Time (seconds)
C
u
r
r
e
n
t

d
e
n
s
i
t
y

(
A
/
c
m
2
)
2213
2209
2
2
0
5
2
2
0
7
Fig. 6. Chronoamperometric behaviour of the alloys in 3.5% NaCl under applied
potential of 300 mV.
J.H. Potgieter et al. / Corrosion Science 50 (2008) 25722579 2577
identied by XRD analysis after corrosion. This corroborates the
observations on the ability of nickel to form a stable passive lm
on alloys surfaces [2729]. Munoz et al. [22] noted that these lms
do not considerably improve the passivation properties in halide
environments, as halide ions can be adsorbed on the lm and re-
place the oxygen position in the lm, forming a soluble metal ha-
lide and destroying the lm. However, the highest pitting
resistance exhibited by 2213 can probably be largely attributed
to its highest nickel contents.
The considerable improvement of the pitting properties of the
duplex stainless steels investigated in this study could also be
attributed to the electrochemical characteristic of nickel that is no-
bler than chromium and iron. Since nickel is less readily oxidized
than iron and chromium, there could be an enrichment of nickel
in its metallic state in the metal closest to the oxide/metal inter-
face, thereby prolonging the passive region [30]. In the presence
of nitrogen, Willenbruch et al. [31] discovered that this enrichment
could assist in the formation of a desirable stable nickel nitride
layer, which could also improve passivation. However, the alloys
used in this study contained low nitrogen that could not have con-
tributed to the increase in pitting corrosion resistance. Hence, it
could be concluded that the high pitting resistance exhibited by al-
loys containing higher nickel contents is primarily due to nickel
addition. This was conrmed by XRD results where nickel was ob-
served to be enriched in chromium oxide. The enrichment of nickel
in the chromium oxide formed could have strengthened the pro-
tective nature of chromium oxide and therefore signicantly im-
prove the resistance of the alloy to further corrosion.
4. Conclusions
The results from this study reveal that increasing nickel con-
tents on 22% Cr duplex stainless steel is very promising for improv-
ing its corrosion resistance in sodium chloride and sulphuric acid
media. The alloys displayed similar passivation behaviour in sul-
phuric acid solution, but large differences in chloride medium.
Resistance to corrosion types was believe to be due to the types
of passivating lms formed in the different media studied. The
improvement on the resistance to a particular type of corrosion
through nickel additions investigated in this study could be con-
cluded to be attributed to the effects of nickel on two major met-
allurgical controlling factors. Uniform corrosion behaviour of the
alloys could be concluded to be predominantly controlled by phase
composition and ratio while pitting resistance was chiey con-
trolled by nickel contents. In making a choice on selecting suitable
and appropriate alloy for specied condition, alloy 2209 proved
best as highest resistance to uniform corrosion while 2213 is most
excellent in terms of highest pitting resistance. Since the inuence
of nickel on the corrosion behaviour of these alloys shows a reec-
tion of microstructural integrity, their physical metallurgy needs to
be fully understood for proper microstructural and phase manipu-
lations and modications. These could be achieved through proper
selection of heat treatment parameters.
Acknowledgement
The authors wish to acknowledge the nancial support received
from the DST/NRF Centre of Excellence in Strong Materials of the
University of the Witwatersrand, Johannesburg for this study.
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